EP2691175A1 - Compositions contenant des catalyseurs phosphonates et procédés pour la préparation et l'utilisation des compositions - Google Patents

Compositions contenant des catalyseurs phosphonates et procédés pour la préparation et l'utilisation des compositions

Info

Publication number
EP2691175A1
EP2691175A1 EP12710618.5A EP12710618A EP2691175A1 EP 2691175 A1 EP2691175 A1 EP 2691175A1 EP 12710618 A EP12710618 A EP 12710618A EP 2691175 A1 EP2691175 A1 EP 2691175A1
Authority
EP
European Patent Office
Prior art keywords
ingredient
composition
clear
group
nacure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12710618.5A
Other languages
German (de)
English (en)
Inventor
Simon Cook
Geraldine Durand
Thomas Easton
Victoria JAMES
Sarah O'hare
Avril Surgenor
Richard Taylor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Publication of EP2691175A1 publication Critical patent/EP2691175A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids

Definitions

  • Condensation reaction curable compositions contain new phosphonate catalysts.
  • the compositions can cure without the presence of conventional catalysts, such as organotin catalysts.
  • Tin compounds are useful as catalysts for the condensation cure of many polyorganosiloxane compositions, including adhesives, sealants, low permeability products such as those useful in insulating glass applications, coatings, and silicone elastomer latices.
  • Organotin compounds for condensation reaction catalysis are those where the valence of the tin is either +4 or +2, i.e. , Tin (IV) compounds or Tin (II) compounds.
  • tin (IV) compounds include stannic salts of carboxylic acids such as dibutyl tin dilaurate (DBTDL), dimethyl tin dilaurate, di-(n-butyl)tin bis-ketonate, dibutyl tin diacetate, dibutyl tin maleate, dibutyl tin diacetylacetonate, dibutyl tin dimethoxide,
  • DBTDL dibutyl tin dilaurate
  • dimethyl tin dilaurate di-(n-butyl)tin bis-ketonate
  • dibutyl tin diacetate dibutyl tin maleate
  • dibutyl tin diacetylacetonate dibutyl tin dimethoxide
  • Tin (IV) compounds are known in the art and are commercially available, such as Metatin® 740 and Fascat® 4202 from Acima Specialty Chemicals of Switzerland, Europe, which is a business unit of The Dow Chemical Company.
  • tin (II) compounds include tin (II) salts of organic carboxylic acids such as tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, tin (II) dilaurate, stannous salts of carboxylic acids such as stannous octoate, stannous oleate, stannous acetate, stannous laurate, stannous stearate, stannous naphthanate, stannous hexoate, stannous succinate, stannous caprylate, and a combination thereof.
  • REACH Registration, Evaluation, Authorization and Restriction of Chemical
  • tin based catalysts which are used in many condensation reaction curable polyorganosiloxane products such as sealants and coatings, are to be phased out. Therefore, there is an industry need to replace conventional tin catalysts in condensation reaction curable compositions.
  • a composition capable of reacting via condensation reaction comprises:
  • the Ingredient (A) is capable of catalyzing condensation reaction of the
  • disclosure of a range of, for example, 2.0 to 4.0 includes the subsets of, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed in the range.
  • disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein.
  • a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an alkaryl group includes the member alkyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein.
  • Free of means that the composition contains a non-detectable amount of the ingredient, or the composition contains an amount of the ingredient insufficient to change the tack free time measured by the method in Reference Example 2 as compared to the same composition with the ingredient omitted.
  • the composition described herein may be free of tin catalysts.
  • Free of tin catalysts means that the composition contains a non- detectable amount of a tin catalyst capable of catalyzing a condensation reaction with the hydrolyzable groups on other ingredients in the composition, or the composition contains an amount of a tin catalyst insufficient to change the tack free time measured by the method in Reference Example 2, as compared to the same composition with the tin catalyst omitted.
  • the composition may be free of titanium catalysts.
  • “Free of titanium catalysts” means that the composition contains a non-detectable amount of a titanium catalyst capable of catalyzing a condensation reaction with the hydrolyzable groups on other ingredients in the composition, or the composition contains an amount of a titanium catalyst insufficient to change the tack free time measured by the method in Reference Example 2, as compared to the same composition with the titanium catalyst omitted.
  • the composition described herein may be free of metal condensation reaction catalysts.
  • Free of metal condensation reaction catalysts means that the composition contains a non-detectable amount of a compound of a Group 3 a, 4a, 5 a, or 4b metal of the periodic table, which is capable of catalyzing a condensation reaction, such as compounds of Al, Bi, Sn, Ti, and/or Zr; or an amount of such a metal condensation reaction catalyst insufficient to change the tack free time measured by the method in Reference Example 2 as compared to the same composition with the metal condensation reaction catalyst omitted.
  • a condensation reaction such as compounds of Al, Bi, Sn, Ti, and/or Zr
  • Non-functional means that the ingredient, e.g. , a polyorganosiloxane, does not participate in a condensation reaction.
  • centiPoise centiPoise
  • DP centiPoise
  • FTIR Fourier transform infrared spectrophotometry
  • GPC gel permeation
  • Mn refers to number average molecular weight of a polymer. Mn may be measured using GPC.
  • Mw refers to weight average molecular weight of a polymer.
  • NMR refers to nuclear magnetic resonance.
  • composition that is capable of reacting by condensation reaction (composition) comprises:
  • composition a base polymer having an average, per molecule, of one or more hydrolyzable substituents.
  • the composition may optionally further comprise one or more additional ingredients.
  • the one or more additional ingredients may be distinct from ingredients (A) and
  • Suitable additional ingredients are exemplified by (C) a crosslinker; (D) a drying agent; (E) an extender, a plasticizer, or a combination thereof; (F) a filler; (G) a filler treating agent; (H) a biocide; (J) a flame retardant; (K) a surface modifier; (L) a chain lengthener; (M) an endblocker; (N) a nonreactive binder; (O) an anti-aging additive; (P) a water release agent; (Q) a pigment; (R) a rheological additive; (S) a solvent; (T) a tackifying agent; and a combination thereof.
  • Ingredient (A) comprises a phosphonate.
  • the phosphonate may comprise a monomeric phosphonate, a polymeric phosphonate, or a combination thereof.
  • the phosphonate may comprise an organic phosphonate, a silyl phosphonate, or a combination thereof.
  • the phosphonate may have average general formula (i):
  • each A is independently a monovalent hydrocarbon group
  • each A is independently selected from a hydrogen atom, a monovalent organic group, a silyl
  • each A is independently a monovalent hydrocarbon group, or a siloxane group
  • each group A is independently a monovalent
  • each A is independently a hydrogen atom, a monovalent hydrocarbon group, or a silyl group.
  • a , and A include, but are not limited to, alkyl such as methyl, ethyl, propyl, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undecyl, and octadecyl; alkenyl such as vinyl, allyl, propenyl, and hexenyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as phenyl, tolyl, and xylyl; alkaryl such as benzyl; and aralkyl such as 2-phenylethyl.
  • alkyl such as methyl, ethyl, propyl, pentyl, hexyl, heptyl, ethylhexyl, octyl, decyl, dodecyl, undec
  • Subscript a may have a value ranging from 0 to 50, alternatively 0 to 20.
  • ingredient (A) is a monomeric phosphonate
  • subscript a has a value of 0.
  • each A ⁇ is independently an alkyl group of 1 to 8 carbon atoms or an alkenyl group of 1 to 8 carbon
  • each A is independently a hydrogen atom, an alkyl group of 1 to 4 carbon atoms,
  • each A is independently an alkyl group of 1 to 4 carbon atoms.
  • alkyl groups examples include methyl, ethyl, propyl, butyl,
  • each A and each A may be independently
  • each A may be independently selected
  • each A may be independently selected
  • each A may be independently selected from a hydrogen atom or a monovalent hydrocarbon group, such as alkyl or alkenyl; alternatively alkyl.
  • average formula (i) can represent an equilibrium mixture of species, where at least some of the molecules of formula (i) present contain a silyl group and some of the molecules of formula (i) do not contain a silyl group.
  • Ingredient (A) may comprise diethenyl-diphosphonic acid, vinylphosphonic acid, bis(trimethylsilyl) vinylphosphonate, trimethylsilyl vinylphosphonic acid,
  • ingredient (A) may comprise a mixture of bis(trimethylsilyl) octylphosphonate, trimethylsilyl octylphosphonate, and octylphosphonic acid.
  • Phosphonates are commercially available.
  • DOW CORNING® 4-6085 is a mixture comprising monomeric silyl phosphonate and monomeric organic phosphonate species
  • DOW CORNING® 4-6025 is a mixture comprising monomeric and polymeric phosphonate species
  • DOW CORNING® 4-6035 is also a commercially available phosphonate.
  • These phosphonates are all available from Dow Corning Corporation of Midland, Michigan, U.S.A. Dimethyl methylphosphonate is also commercially available.
  • the composition may contain one single phosphonate condensation reaction catalyst.
  • the composition may comprise two or more phosphonate
  • the composition may be free of tin catalysts.
  • the composition may be free of titanium catalysts.
  • the composition may be free of metal condensation reaction catalysts.
  • the composition may be free of any phosphonate that would catalyze the condensation reaction of the hydrolyzable groups on ingredient (B) other than the phosphonate condensation reaction catalyst defined herein as ingredient (A).
  • the composition may be free of any ingredient that would catalyze the condensation reaction of the hydrolyzable groups on ingredient (B) other than the phosphonate condensation reaction catalyst defined herein as ingredient (A).
  • Ingredient (B) is a base polymer.
  • Ingredient (B) comprises a polymer backbone having an average, per molecule, of one or more hydrolyzable substituents covalently bonded thereto.
  • the one or more hydrolyzable substituents are silyl hydrolyzable substituents.
  • the polymer backbone may be selected from a polyorganosiloxane such as a polydiorganosiloxane, an organic polymer backbone, or a silicone-organic copolymer backbone.
  • the polymer backbone of ingredient (B) may be a
  • the polymer backbone of ingredient (B) may be a polyorganosiloxane backbone.
  • the hydrolyzable substituents are exemplified by halogen atoms; amido groups such as acetamido groups, benzamido groups, or methylacetamido groups; acyloxy groups such as acetoxy groups; hydrocarbonoxy groups such as alkoxy groups or alkenyloxy groups; amino groups; aminoxy groups; hydroxyl groups; mercapto groups; oximo groups; ketoximo groups; alkoxysilylhydrocarbylene groups; or a combination thereof.
  • ingredient (B) may have an average of two or more hydrolyzable substituents per molecule.
  • the hydrolyzable substituent in ingredient (B) may be located at terminal, pendant, or both terminal and pendant positions on the polymer backbone.
  • the hydrolyzable substituent in ingredient (B) may be located at one or more terminal positions on the polymer backbone.
  • Ingredient (B) may comprise a linear, branched, cyclic, or resinous structure.
  • ingredient (B) may comprise a linear, branched or cyclic structure.
  • ingredient (B) may comprise a linear or branched structure.
  • ingredient (B) may comprise a linear structure.
  • ingredient (B) may comprise a linear structure and a resinous structure.
  • Ingredient (B) may comprise a homopolymer or a copolymer or a combination thereof.
  • Ingredient (B) may have the hydrolyzable substituents contained in groups of the formula (ii):
  • each D independently represents an oxygen atom, a divalent organic group, a silicone organic group, or a combination of a divalent hydrocarbon group and a divalent siloxane group
  • each X independently represents a hydrolyzable substituent
  • each R independently represents a monovalent hydrocarbon group
  • subscript c represents 0, 1, 2, or 3
  • subscript a represents 0, 1, or 2
  • subscript b has a value of 0 or greater, with the proviso that the sum of (a + c) is at least 1, such that, on average, at least one X is present in the formula.
  • subscript b may have a value ranging from 0 to 18.
  • each D may be independently selected from an oxygen atom and a divalent hydrocarbon group.
  • each D may be an oxygen atom.
  • each D may be a divalent hydrocarbon group exemplified by an alkylene group such as ethylene, propylene, butylene, or hexylene; an arylene group such as phenylene, or an alkylarylene group such as: or .
  • an instance of D may be an oxygen atom while a different instance of D is a divalent hydrocarbon group.
  • each X may be selected from the group consisting of an alkoxy group; an alkenyloxy group; an amido group, such as an acetamido, a methylacetamido group, or benzamido group; an acyloxy group such as acetoxy; an amino group; an aminoxy group; a hydroxyl group; a mercapto group; an oximo group; a ketoximo group; and a halogen atom.
  • each X may be selected from the group consisting of an alkoxy group, an amido group, an acyloxy group, an amino group, a hydroxyl group, and an oximo group.
  • each R in the formula above may be independently selected from alkyl groups of 1 to 20 carbon atoms, aryl groups of 6 to 20 carbon atoms, and aralkyl groups of 7 to 20 carbon atoms.
  • subscript b may be 0.
  • Ingredient (B) may comprise the groups described by formula (ii) above in an amount of the base polymer ranging from 0.2 mol % to 10 mol , alternatively 0.5 mol % to 5 mol , alternatively 0.5 mol % to 2.0 mol , alternatively 0.5 mol % to 1.5 mol , and alternatively 0.6 mol % to 1.2 mol .
  • Ingredient (B) may have a polyorganosiloxane backbone with a linear structure, i.e., a polydiorganosiloxane backbone.
  • ingredient (B) may comprise an alkoxy-endblocked polydiorganosiloxane, an alkoxysilylhydrocarbylene-endblocked polydiorganosiloxane, a hydroxyl-endblocked polydiorganosiloxane, or a combination thereof.
  • Ingredient (B) may comprise a polydiorganosiloxane of formula (I):
  • each R is independently a hydrolyzable substituent, each R is independently a
  • each R is independently an oxygen atom or a divalent hydrocarbon group
  • each subscript d is independently 1, 2, or 3
  • subscript e is an integer having a value sufficient to provide the polydiorganosiloxane with a viscosity of at least 100 mPa-s at 25 °C and/or a DP of at least 87.
  • DP may be measured by GPC using polystyrene calibration.
  • subscript e may have a value ranging from 1 to 200,000.
  • Suitable hydrolyzable substituents for R ⁇ include, but are not limited to, the hydrolyzable substituents described above for group X.
  • the hydrolyzable substituents for R ⁇ may be selected from a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, and a methylacetamido group.
  • Suitable organic groups for R include, but are not limited to, monovalent organic groups such as hydrocarbon groups and halogenated hydrocarbon groups. Examples of
  • monovalent hydrocarbon groups for R include, but are not limited to, alkyl such as methyl, ethyl, propyl, pentyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as phenyl, tolyl, xylyl, and benzyl; and aralkyl such as
  • Examples of monovalent halogenated hydrocarbon groups for R include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl groups; fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4- trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3- nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl; chlorinated cycloalkyl groups such as 2,2- dichlorocyclopropyl, 2,3-dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2,2- difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocycl
  • R examples include, but are not limited to, hydrocarbon groups substituted with oxygen atoms such as glycidoxyalkyl, and hydrocarbon groups substituted with nitrogen atoms such as aminoalkyl and cyano-functional
  • each R may be an alkyl group such as methyl.
  • Ingredient (B) may comprise an ⁇ , ⁇ -difunctional-polydiorganosiloxane when, in
  • each subscript d is 1 and each R is an oxygen atom.
  • each R is an oxygen atom.
  • 1 2 2 2 1 1 2 ingredient (B) may have formula (II): R R 2SiO-(R 2SiO) e '-SiR 2R , where R and R are as described above and subscript e' is an integer having a value sufficient to give the polydiorganosiloxane of formula (II) the viscosity described above.
  • subscript e' may have a value ranging from 1 to 200,000, alternatively 50 to 1,000, and alternatively 200 to 700.
  • ingredient (B) may comprise a hydroxyl-functional
  • each R may be an alkyl group such as methyl
  • subscript e' may have a value such that the hydroxyl functional polydiorganosiloxane has a viscosity of at least 100 mPa-s at 25 °C.
  • subscript e' may have a value ranging from 50 to 700.
  • Exemplary hydroxyl-endblocked polydiorganosiloxanes are hydroxyl-endblocked
  • Hydroxyl-endblocked polydiorganosiloxanes suitable for use as ingredient (B) may be prepared by methods known in the art, such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic
  • ingredient (B) may comprise an alkoxysilylhydrocarbylene-
  • each R is divalent hydrocarbon group or a combination of a divalent hydrocarbon group and a divalent siloxane group.
  • Each R may be an alkylene group such as ethylene, propylene, or hexylene; an arylene group such as phenylene, or an alkylarylene group such as: or .
  • each R and each R may be alkyl, each R may be alkylene such as ethylene, and each subscript d may be 3.
  • Alkoxysilylhydrocarbylene-endblocked polydiorganosiloxanes may be prepared by reacting a vinyl-terminated, polydimethylsiloxane with
  • ingredient (B) may comprise a moisture-curable, silane-functional, organic polymer.
  • the organic polymer may be a polymer in which at least half the atoms in the polymer backbone are carbon atoms with terminal moisture curable silyl groups containing hydrolyzable substituents bonded to silicon atoms.
  • the organic polymer can, for example, be selected from hydrocarbon polymers, polyethers, acrylate polymers, polyurethanes and polyureas.
  • Ingredient (B) may be elastomeric, i.e. , have a glass transition temperature (Tg) less than 0 °C.
  • Tg glass transition temperature
  • ingredient (B) may be distinguished from semi-crystalline and amorphous polyolefins (e.g. , alpha-olefins), commonly referred to as thermoplastic polymers.
  • Ingredient (B) may comprise a silylated poly-alpha-olefin, a silylated copolymer of an iso-mono-olefin and a vinyl aromatic monomer, a silylated copolymer of a diene and a vinyl aromatic monomer, a silylated copolymer of an olefin and a diene (e.g.
  • silylated butyl rubber prepared from polyisobutylene and isoprene, which may optionally be halogenated), or a combination thereof (silylated copolymers), a silylated homopolymer of the iso-mono- olefin, a silylated homopolymer of the vinyl aromatic monomer, a silylated homopolymer of the diene (e.g., silylated polybutadiene or silylated hydrogenated polybutadiene), or a combination thereof (silylated homopolymers) or a combination silylated copolymers and silylated homopolymers.
  • silylated butyl rubber prepared from polyisobutylene and isoprene, which may optionally be halogenated
  • silylated copolymers a silylated homopolymer of the iso-mono- olefin
  • a silylated homopolymer of the vinyl aromatic monomer
  • silylated copolymers and silylated homopolymers are referred to collectively as 'silylated polymers' .
  • the silylated polymer may optionally contain one or more halogen groups, particularly bromine groups.
  • Examples of suitable mono-iso-olefins include, but are not limited to, isoalkylenes such as isobutylene, isopentylene, isohexylene, and isoheptylene; alternatively isobutylene.
  • Examples of suitable vinyl aromatic monomers include but are not limited to alkylstyrenes such as alpha-methylstyrene, t-butylstyrene, and para-methylstyrene; alternatively para- methylstyrene.
  • Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl; alternatively methyl.
  • alkenyl groups include, vinyl, allyl, propenyl, butenyl, and hexenyl; alternatively vinyl.
  • the silylated organic polymer may have Mn ranging from 20,000 to 500,000, alternatively 50,000- 200,000, alternatively 20,000 to 100,000, alternatively 25,000 to 50,000, and alternatively 28,000 to 35,000; where values of Mn were measured by Triple Detection Size Exclusion Chromatography and calculated on the basis of polystyrene molecular weight standards.
  • silylated poly- alpha-olef ins are known in the art and are commercially available.
  • examples include the condensation reaction curable silylated polymers marketed as VESTOPLAST®, which are commercially available from Degussa AG Coatings & Colorants of Marl, Germany, Europe.
  • a method for preparing the silylated copolymers involves contacting i) an olefin copolymer having at least 50 mole % of an iso-mono-olefin having 4 to 7 carbon atoms and a vinyl aromatic monomer; ii) a silane having at least two hydrolyzable groups and at least one olefinically unsaturated hydrocarbon or hydrocarbonoxy group; and iii) a free radical generating agent.
  • silylated copolymers may be prepared by a method comprising conversion of commercially available hydroxylated polybutadienes (such as those commercially available from Cray Valley SA of Paris, France, under trade names Poly BD and Krasol) by known methods (e.g. , reaction with isocyanate functional alkoxysilane, reaction with allylchloride in presence of Na followed by hydrosilylation).
  • commercially available hydroxylated polybutadienes such as those commercially available from Cray Valley SA of Paris, France, under trade names Poly BD and Krasol
  • known methods e.g. , reaction with isocyanate functional alkoxysilane, reaction with allylchloride in presence of Na followed by hydrosilylation.
  • silyl modified hydrocarbon polymers include silyl modified polyisobutylene, which is available commercially in the form of telechelic polymers.
  • Silyl modified polyisobutylene can, for example, contain curable silyl groups derived from a silyl-substituted alkyl acrylate or methacrylate monomer such as a
  • dialkoxyalkylsilylpropyl methacrylate or trialkoxysilylpropyl methacrylate which can be reacted with a polyisobutylene prepared by living anionic polymerisation, atom transfer radical polymerization or chain transfer polymerization.
  • ingredient (B) may comprise a polyether.
  • polyether is a polyoxyalkylene polymer comprising recurring oxyalkylene units of the formula (-CtH2t-0-) where subscript t is an integer with a value ranging from 2 to 4.
  • Polyoxyalkylene polymers typically have terminal hydroxyl groups, and can readily be terminated with silyl groups having hydrolyzable substituents bonded to silicon atoms, for example by reaction with an excess of an alkyltrialkoxysilane to introduce terminal alkyldialkoxysilyl groups.
  • polymerization may occur via a hydrosilylation type process.
  • Polyoxyalkylenes comprising mostly oxypropylene units may have properties suitable for many sealant uses.
  • Polyoxyalkylene polymers, particularly polyoxypropylenes, having terminal alkyldialkoxysilyl or trialkoxysilyl groups may react with each other in the presence of ingredient (A) and moisture. These base polymers may not require a separate crosslinker in the composition.
  • the organic polymer having hydrolysable silyl groups can alternatively be an acrylate polymer, that is an addition polymer of acrylate and/or methacrylate ester monomers, which may comprise at least 50 % of the monomer units in the acrylate polymer.
  • acrylate ester monomers are n-butyl, isobutyl, n-propyl, ethyl, methyl, n-hexyl, n-octyl and 2-ethylhexyl acrylates.
  • methacrylate ester monomers are n-butyl, isobutyl, methyl, n-hexyl, n-octyl, 2-ethylhexyl and lauryl methacrylates.
  • the acrylate polymer may have a glass transition temperature (Tg) below ambient temperature; and acrylate polymers may form lower Tg polymers than methacrylate polymers.
  • An exemplary acrylate polymer is polybutyl acrylate.
  • the acrylate polymer may contain lesser amounts of other monomers such as styrene, acrylonitrile or acrylamide.
  • the acrylate polymer can be prepared by various methods such as conventional radical polymerization, or living radical polymerization such as atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, or anionic polymerization including living anionic polymerization.
  • the curable silyl groups can, for example, be derived from a silyl-substituted alkyl acrylate or methacrylate monomer.
  • Hydrolysable silyl groups such as dialkoxyalkylsilyl or trialkoxysilyl groups can, for example, be derived from a
  • dialkoxyalkylsilylpropyl methacrylate or trialkoxysilylpropyl methacrylate When the acrylate polymer has been prepared by a polymerization process which forms reactive terminal groups, such as atom transfer radical polymerization, chain transfer polymerization, or living anionic polymerization, it can readily be reacted with the silyl-substituted alkyl acrylate or methacrylate monomer to form terminal hydrolyzable silyl groups.
  • Silyl modified polyurethanes or polyureas can, for example, be prepared by the reaction of polyurethanes or polyureas having terminal ethylenically unsaturated groups with a silyl monomer containing hydrolyzable groups and a Si-H group, for example a
  • dialkoxyalkylsilicon hydride or trialkoxysilicon hydride dialkoxyalkylsilicon hydride or trialkoxysilicon hydride.
  • the base polymer may have a silicone-organic block copolymer backbone, which comprises at least one block of polyorganosiloxane groups and at least one block of an organic polymer chain.
  • the polyorganosiloxane groups may comprise groups of formula
  • each R is independently an organic group such as a hydrocarbon group having from 1 to 18 carbon atoms, a halogenated hydrocarbon group having from 1 to 18 carbon atoms such as chloromethyl, perfluorobutyl, trifluoroethyl, and nonafluorohexyl, a hydrocarbonoxy group having up to 18 carbon atoms, or another organic group exemplified by an oxygen atom containing group such as (meth)acrylic or carboxyl; a nitrogen atom containing group such as amino-functional groups, amido-functional groups, and cyano- functional groups; a sulfur atom containing group such as mercapto groups; and subscript f has, on average, a value ranging from 1 to 3, alternatively 1.8 to 2.2.
  • each R may be a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group; and subscript f may be 0, 1 or 2. Examples of groups
  • R suitable for R include methyl, ethyl, propyl, butyl, vinyl, cyclohexyl, phenyl, tolyl group, a propyl group substituted with chlorine or fluorine such as 3,3,3-trifluoropropyl, chlorophenyl, beta-(perfluorobutyl)ethyl or chlorocyclohexyl group.
  • the organic blocks in the polymer backbone may comprise, for example, polystyrene and/or substituted polystyrenes such as poly(a-methylstyrene), poly(vinylmethylstyrene), dienes, poly(p-trimethylsilylstyrene) and poly(p-trimethylsilyl-a-methylstyrene).
  • Other organic groups, which may be incorporated in the polymer backbone may include acetylene terminated oligophenylenes, vinylbenzyl terminated aromatic polysulphones oligomers, aromatic polyesters, aromatic polyester based monomers, poly alky lenes, polyurethanes, aliphatic polyesters, aliphatic polyamides and aromatic polyamides.
  • ingredient (B) may comprise a silicone resin, in addition to, or instead of, one of the polymers described above for ingredient (B).
  • Suitable silicone resins are exemplified by an MQ resin, which comprises siloxane units of the formulae:
  • R W R (3_ w )SiO /2 and S1O4/2 where R and R are monovalent organic groups, such as monovalent hydrocarbon groups exemplified by alkyl such as methyl, ethyl, propyl, pentyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as phenyl, tolyl, xylyl, and benzyl; and aralkyl such as 2-phenylethyl; halogenated hydrocarbon group exemplified by chlorinated alkyl groups such as
  • chloromethyl and chloropropyl groups fluorinated alkyl groups such as fluoromethyl, 2- fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3, 3-pentafluorobutyl,
  • each R and each R may be an alkyl group.
  • the MQ resin may have a molar ratio of M units to Q units (M:Q) ranging from 0.5: 1
  • Si(OSiMe3)4 present in the initial silicone resin, in addition to the total hydroxyl content of the silicone resin.
  • the MQ silicone resin is soluble in solvents such as liquid hydrocarbons exemplified by benzene, toluene, xylene, and heptane, or in liquid organosilicon compounds such as a low viscosity cyclic and linear polydiorganosiloxanes.
  • the MQ silicone resin may contain 2.0 % or less, alternatively 0.7 % or less, alternatively 0.3 % or less, of terminal units represented by the formula X"SiC>3/2, where X" represents hydroxyl or a hydrolyzable group such as alkoxy such as methoxy and ethoxy; alkenyloxy such as isopropenyloxy; ketoximo such as methyethylketoximo; carboxy such as acetoxy; amidoxy such as acetamidoxy; and aminoxy such as ⁇ , ⁇ -dimethylaminoxy.
  • the concentration of silanol groups present in the silicone resin can be determined using FTIR.
  • the Mn required to achieve the desired flow characteristics of the MQ silicone resin will depend at least in part on the molecular weight of the silicone resin and the type of
  • the Mn of the MQ silicone resin is typically greater than 3,000, more typically from 4500 to 7500.
  • the MQ silicone resin can be prepared by any suitable method. Silicone resins of this type have reportedly been prepared by cohydrolysis of the corresponding silanes or by silica hydrosol capping methods known in the art. Briefly stated, the method involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a combination thereof, and recovering a product comprising M and Q units (MQ resin). The resulting MQ resins may contain from 2 to 5 percent by weight of silicon-bonded hydroxyl groups.
  • the intermediates used to prepare the MQ silicone resin may be triorganosilanes of
  • R 3S1X where X represents a hydrolyzable group, as described above for ingredient (B), and either a silane with four hydrolyzable groups such as halogen, alkoxy or hydroxyl, or an alkali metal silicate such as sodium silicate.
  • X represents a hydrolyzable group, as described above for ingredient (B), and either a silane with four hydrolyzable groups such as halogen, alkoxy or hydroxyl, or an alkali metal silicate such as sodium silicate.
  • HOR SiOi/2 or HOS1O3/2 groups in the silicone resin be below 0.7 % by weight of the total weight of the silicone resin, alternatively below 0.3 .
  • Silicon-bonded hydroxyl groups formed during preparation of the silicone resin are converted to trihydrocarbylsiloxy groups or a hydrolyzable group by reacting the silicone resin with a silane, disiloxane or disilazane containing the appropriate terminal group.
  • Silanes containing hydrolyzable groups may be added in excess of the quantity required to react with the silicon-bonded hydroxyl groups of the silicone resin.
  • MQ resins are commercially available from sources such as Dow Corning Corporation of Midland, MI, U.S.A., Momentive Performance Materials of Albany, N.Y., U.S.A., and Bluestar Silicones USA Corp. of East Brunswick, N.J., U.S.A.
  • Surfactant, DOW CORNING® 7466 Resin, and DOW CORNING® 7366 Resin are suitable for use in the methods described herein.
  • MQ resins are disclosed in US Patent 5,082,706 to Tangney.
  • a resin containing M, T, and Q units may be used, such as DOW CORNING® MQ-1640 Flake Resin, which is also commercially available from Dow Corning Corporation.
  • Such resins may be supplied in organic solvent.
  • the silicone resin may comprise a silsesquioxane resin, i. e. , a resin
  • Each R may be independently selected from a hydrogen atom and a monovalent organic group, such as a monovalent hydrocarbon group exemplified by alkyl such as methyl, ethyl, propyl, pentyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl such as phenyl, tolyl, xylyl, and benzyl; and aralkyl such as 2-phenylethyl; halogenated hydrocarbon group exemplified by chlorinated alkyl groups such as chloromethyl and chloropropyl groups; a fluorinated alkyl group such as fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,4,
  • Silsesquioxane resins suitable for use herein are known in the art and are commercially available.
  • a methylmethoxysiloxane methylsilsesquioxane resin having a DP of 15 and a weight average molecular weight (Mw) of 1200 is commercially available as DOW CORNING® US-CF 2403 Resin from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • the silsesquioxane resin may have
  • phenylsilsesquioxane units phenylsilsesquioxane units, methylsilsesquioxane units, or a combination thereof.
  • Such resins are known in the art and are commercially available as DOW CORNING® 200 Flake resins, also available from Dow Corning Corporation.
  • the silicone resin may
  • DT resins are known in the art and are commercially available, for example, methoxy functional DT resins include DOW CORNING® 3074 and DOW CORNING® 3037 resins; and silanol functional resins include DOW CORNING® 800 Series resins, which are also commercially available from Dow Corning Corporation.
  • Other suitable resins include DT resins containing methyl and phenyl groups.
  • the amount of silicone resin added to the composition will vary depending on the end use of the composition. For example, when the reaction product of the composition is a gel, little or no silicone resin may be added. However, the amount of silicone resin in the composition may range from 0 % to 90 , alternatively 0.1 % to 50 , based on the weight of all ingredients in the composition.
  • the amount of ingredient (B) will depend on various factors including the end use of the reaction product of the composition, the type of base polymer selected for ingredient (B), and the type(s) and amount(s) of any additional ingredient(s) present, if any. However, the amount of ingredient (B) may range from 0.01 % to 99 , alternatively 10 % to 95 , alternatively 10 % to 65 % of the composition.
  • Ingredient (B) can be one single base polymer or a combination comprising two or more base polymers that differ in at least one of the following properties: average molecular weight, hydrolyzable substituents, siloxane units, sequence, and viscosity.
  • composition further may further comprise an additional base polymer having an average of more than two hydrolyzable substituents per molecule, or ingredient (C) a crosslinker, or both.
  • Ingredient (A) may be selected based on various factors including the type of polymer backbone and/or hydrolyzable groups in ingredient (B). For example, when ingredient (B) has an organic polymer backbone, then ingredient (A) may comprise a polymeric phosphonate. Alternatively, when ingredient (B) has an organic polymer backbone, then ingredient (A) may comprise a combination of a silyl phosphonate and an organic phosphonate. When ingredient (B) has a silicone organic block copolymer backbone, then ingredient (A) may comprise a silyl phosphonate, an organic phosphonate, or a combination thereof. Alternatively, when ingredient (B) has a silicone organic block copolymer backbone, then ingredient (A) may comprise a polymeric phosphonate.
  • ingredient (A) when ingredient (B) has a polyorganosiloxane backbone, ingredient (A) may comprise a phosphonate of formula (i), above. Alternatively, when ingredient (B) has a polyorganosiloxane backbone, ingredient (A) may comprise an organic phosphonate, a silyl phosphonate, or a combination thereof. Alternatively, when ingredient (B) has a
  • ingredient (A) may comprise a combination of an organic phosphonate and a silyl phosphonate.
  • ingredient (B) has a
  • ingredient (A) may comprise a polymeric phosphonate.
  • the composition may optionally further comprise one or more additional ingredients, i.e. , in addition to ingredients (A) and (B) and distinct from ingredients (A) and (B).
  • the additional ingredient if present, may be selected based on factors such as the method of use of the composition and/or the end use of the cured product of the composition.
  • the additional ingredient may be: (C) a crosslinker; (D) a drying agent; (E) an extender, a plasticizer, or a combination thereof; (F) a filler such as (fl) a reinforcing filler, (f2) an extending filler, (f3) a conductive filler (e.g.
  • a biocide such as (hi) a fungicide, (h2) an herbicide, (h3) a pesticide, or (h4) an antimicrobial
  • J a flame retardant
  • K a surface modifier such as (kl) an adhesion promoter or (k2)
  • Ingredient (C) is a crosslinker that may be added to the composition, for example, when ingredient (B) contains an average of only one or two hydrolyzable substituents per molecule and/or to increase crosslink density of the reaction product prepared by
  • ingredient (C) is selected with functionality that will vary depending on the degree of crosslinking desired in the reaction product of the composition and such that the reaction product does not exhibit too much weight loss from by-products of the condensation reaction. Generally, the selection of ingredient (C) is made such that the composition remains sufficiently reactable to be useful during storage for several months in a moisture impermeable package. The exact amount of ingredient (C) will vary depending on factors including the type of base polymer and crosslinker selected, the reactivity of the hydrolyzable substituents on the base polymer and crosslinker, and the desired crosslink density of the reaction product. However, the amount of crosslinker may range from 0.5 to 100 parts based on 100 parts by weight of ingredient (B).
  • Ingredient (C) may comprise a silane crosslinker having hydrolyzable groups or partial or full hydrolysis products thereof.
  • Ingredient (C) has an average, per molecule, of greater than two substituents reactive with the hydrolyzable substituents on ingredient (B).
  • suitable silane crosslinkers for ingredient (C) may have the general formula (III)
  • each R is a hydrolyzable substituent, which may be the same as X described
  • each R may be, for example, a halogen atom, an acetamido group, an acyloxy group such as acetoxy, an alkoxy group, an amido group, an amino group, an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, or a methylacetamido group; and each instance of subscript k may be 0, 1, 2, or 3.
  • subscript k has an average value greater than 2.
  • subscript k may have a
  • each R may be independently selected from hydroxyl, alkoxy, acetoxy, amide, or oxime.
  • ingredient (C) may be selected from an acyloxysilane, an alkoxysilane, a ketoximosilane, and an oximosilane.
  • a trialkoxysilane such as an alkyltrialkoxysilane
  • tetraalkoxysilane or partial or full hydrolysis products thereof, or another combination thereof.
  • suitable trialkoxysilanes include methyltrimethoxysilane,
  • methyltriethoxysilane ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, and a combination thereof, and alternatively methyltrimethoxysilane.
  • suitable tetraalkoxysilanes include tetraethoxysilane.
  • the amount of the alkoxysilane that is used in the curable silicone composition may range from 0.5 to 15, parts by weight per 100 parts by weight of ingredient (B).
  • Ingredient (C) may comprise an acyloxysilane, such as an acetoxysilane.
  • Acetoxysilanes include a tetraacetoxysilane, an organotriacetoxysilane, a
  • the acetoxysilane may contain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tertiary butyl; alkenyl groups such as vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, or xylyl; aralkyl groups such as benzyl or 2-phenylethyl; and fluorinated alkyl groups such as 3,3,3-trifluoropropyl.
  • alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tertiary butyl
  • alkenyl groups such as vinyl, allyl, or hexenyl
  • aryl groups such as phenyl, tolyl, or xylyl
  • aralkyl groups such as benzyl or 2-phenylethyl
  • fluorinated alkyl groups such
  • acetoxysilanes include, but are not limited to, tetraacetoxysilane,
  • ingredient (C) may comprise organotriacetoxysilanes, for example mixtures comprising methyltriacetoxysilane and ethyltriacetoxysilane.
  • the amount of the acetoxysilane that is used in the curable silicone composition may range from 0.5 to 15 parts by weight per 100 parts by weight of ingredient (B); alternatively 3 to 10 parts by weight of acetoxysilane per 100 parts by weight of ingredient (B).
  • Examples of silanes suitable for ingredient (C) containing both alkoxy and acetoxy groups that may be used in the composition include methyldiacetoxymethoxysilane, methylacetoxydimethoxysilane, vinyldiacetoxymethoxysilane, vinylacetoxydimethoxysilane, methyldiacetoxyethoxysilane, metylacetoxydiethoxysilane, and combinations thereof.
  • Suitable oximosilanes for ingredient (C) include alkyltrioximosilanes such as methyltrioximosilane, ethyltrioximosilane, propyltrioximosilane, and butyltrioximosilane; alkoxytrioximosilanes such as methoxytrioximosilane, ethoxytrioximosilane, and
  • propoxytrioximosilane or alkenyltrioximosilanes such as propenyltrioximosilane or butenyltrioximosilane; alkenyloximosilanes such as vinyloximosilane; alkenylalkyldioximosilanes such as vinyl methyl dioximosilane, vinyl ethyldioximosilane, vinyl methyldioximosilane, or vinylethyldioximosilane; or combinations thereof.
  • Suitable ketoximosilanes for ingredient (C) include methyl
  • ethoxytri(ethylmethylketoxime)silane methylvinylbis(methylisobutylketoximo)silane, or a combination thereof.
  • ingredient (C) may be polymeric.
  • ingredient (C) may comprise a disilane such as bis(triethoxysilyl)hexane), 1,4- bis[trimethoxysilyl(ethyl)]benzene, and bis[3-(triethoxysilyl)propyl] tetrasulfide
  • Ingredient (C) can be one single crosslinker or a combination comprising two or more crosslinkers that differ in at least one of the following properties: hydrolyzable substituents and other organic groups bonded to silicon, and when a polymeric crosslinker is used, siloxane units, structure, molecular weight, and sequence.
  • Ingredient (D) is a drying agent.
  • the drying agent binds water from various sources.
  • the drying agent may bind by-products of the condensation reaction, such as water and alcohols.
  • adsorbents for ingredient (D) may be inorganic particulates.
  • the adsorbent may have a particle size of 10 micrometers or less, alternatively 5 micrometers or less.
  • the adsorbent may have average pore size sufficient to adsorb water and alcohols, for example 10 A (Angstroms) or less, alternatively 5 A or less, and alternatively 3 A or less.
  • adsorbents include zeolites such as chabasite, mordenite, and analcite; molecular sieves such as alkali metal alumino silicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof.
  • drying agents for ingredient (D) without undue experimentation.
  • drying agents such as silica gel will bind water, while others such as molecular sieves may bind water, alcohols, or both.
  • drying agents examples include dry molecular sieves, such as 3 A (Angstrom) molecular sieves, which are commercially available from Grace Davidson under the trademark SYLOSIV® and from Zeochem of Louisville, Kentucky, U.S.A. under the trade name PURMOL, and 4 A molecular sieves such as Doucil zeolite 4A available from Ineos Silicas of Warrington, England.
  • 3 A (Angstrom) molecular sieves which are commercially available from Grace Davidson under the trademark SYLOSIV® and from Zeochem of Louisville, Kentucky, U.S.A. under the trade name PURMOL
  • 4 A molecular sieves such as Doucil zeolite 4A available from Ineos Silicas of Warrington, England.
  • molecular sieves include MOLSIV ADSORBENT TYPE 13X, 3 A, 4A, and 5 A, all of which are commercially available from UOP of Illinois, U.S.A.; SILIPORITE NK 30AP and 65xP from Atofina of Philadelphia, Pennsylvania, U.S.A.; and molecular sieves available from W.R. Grace of Maryland, U.S.A.
  • the drying agent may bind the water and/or other by-products by chemical means.
  • An amount of a silane crosslinker added to the composition may function as a chemical drying agent.
  • the chemical drying agent may be added to the dry part of a multiple part composition to keep the composition free from water after the parts of the composition are mixed together.
  • alkoxysilanes suitable as drying agents include
  • vinyltrimethoxy silane vinyltriethoxysilane, and combinations thereof.
  • the amount of ingredient (D) depends on the specific drying agent selected.
  • ingredient (D) when ingredient (D) is a chemical drying agent, the amount may range from 0 parts to 5 parts, alternatively 0.1 parts to 0.5 parts.
  • Ingredient (D) may be one chemical drying agent.
  • ingredient (D) may comprise two or more different chemical drying agents.
  • Ingredient (E) is an extender and/or a plasticizer.
  • An extender comprising a nonfunctional polyorganosiloxane may be used in the composition.
  • the non- 22 functional polyorganosiloxane may comprise difunctional units of the formula R 2S1O2/2 23 22 23 and terminal units of the formula R 3S1D' -, where each R and each R are
  • a monovalent organic group such as a monovalent hydrocarbon group exemplified by alkyl such as methyl, ethyl, propyl, and butyl; alkenyl such as vinyl, allyl, and hexenyl; aryl such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as phenylethyl; and D' is an oxygen atom or a divalent group linking the silicon atom of the terminal unit with another silicon atom (such as group D described above for ingredient (B)), alternatively D' is an oxygen atom.
  • Non- functional polyorganosiloxanes are known in the art and are commercially available.
  • Suitable non-functional polyorganosiloxanes are exemplified by, but not limited to, polydimethylsiloxanes.
  • polydimethylsiloxanes include DOW CORNING® 200 Fluids, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A. and may have viscosity ranging from 50 cSt to 100,000 cSt, alternatively 50 cSt to 50,000 cSt, and alternatively 12,500 to 60,000 cSt.
  • An organic plasticizer may be used in addition to, or instead of, the non-functional polyorganosiloxane extender described above.
  • Organic plasticizers are known in the art and are commercially available.
  • the organic plasticizer may comprise a phthalate, a carboxylate, a carboxylic acid ester, an adipate or a combination thereof.
  • the organic plasticizer may be selected from the group consisting of: bis(2-ethylhexyl) terephthalate; bis(2-ethylhexyl)-l,4- benzenedicarboxylate; 2-ethylhexyl methyl- 1,4-benzenedicarboxylate; 1,2
  • cyclohexanedicarboxylic acid dinonyl ester, branched and linear; bis(2-propylheptyl) phthalate; diisononyl adipate; and a combination thereof.
  • the organic plasticizer may have an average, per molecule, of at least one group of
  • R may represent a branched or linear monovalent hydrocarbon group.
  • the monovalent organic group may be a branched or linear monovalent hydrocarbon group such as an alkyl group of 4 to 15 carbon atoms, alternatively 9 to 12 carbon atoms.
  • Suitable plasticizers may be selected from the group consisting of adipates, carboxylates, phthalates, and a combination thereof.
  • the organic plasticizer may have an average, per molecule, of at least two groups of the formula above bonded to carbon atoms in a cyclic hydrocarbon.
  • the organic plasticizer may have general formula:
  • group Z represents a cyclic hydrocarbon group having 3 or more carbon atoms, alternatively 3 to 15 carbon atoms.
  • Subscript s may have a value ranging from 1 to
  • Group Z may be saturated or aromatic.
  • Each R is independently a hydrogen atom or a
  • the monovalent organic group for R may be an alkyl group such as methyl, ethyl, or butyl.
  • R may be an ester functional group.
  • Each R is independently a branched or linear monovalent hydrocarbon group, such as an alkyl group of 4 to 15 carbon atoms.
  • Suitable organic plasticizers are known in the art and are commercially available.
  • the plasticizer may comprise a phthalate, such as: a dialkyl phthalate such as dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, or diisodecyl phthalate (DIDP), bis(2-propylheptyl) phthalate, di(2-ethylhexyl) phthalate, dimethyl phthalate; diethyl phthalate; butyl benzyl phthalate, and bis(2-ethylhexyl) terephthalate; a dicarboxylate such as 1,2,4-benzenetricarboxylic acid, bis(2-ethylhexyl)- 1,4-benzenedicarboxylate; 2-ethylhexyl methyl- 1 ,4-benzenedicarboxylate; 1,2 cyclohexanedicarboxylic
  • hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; tris(2- ethylhexyl) ester; a fatty acid ester; and a combination thereof.
  • suitable plasticizers and their commercial sources include those listed below in the table below. Table of Exemplary Organic Plasticizers and Commercial Sources
  • a polymer plasticizer can be used.
  • the polymer plasticizer include alkenyl polymers obtained by polymerizing vinyl or allyl monomers by means of various methods; polyalkylene glycol esters such as diethylene glycol dibenzoate, triethylene glycol dibenzoate and pentaerythritol ester; polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; poly ethers including poly ether polyols each having a molecular weight of not less than 500 such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polystyrenes such as polystyrene and poly-alpha-methylstyrene; and polybutadiene, polybutene, polyisobutylene, buta
  • the amount of the organic plasticizer may range from 5 to 150 parts by weight based on the combined weights of all ingredients in the composition.
  • the polyorganosiloxane extenders and organic plasticizers described above for ingredient (E) may be used either each alone or in combinations of two or more thereof.
  • a low molecular weight organic plasticizer and a higher molecular weight polymer plasticizer may be used in combination.
  • the exact amount of ingredient (E) used in the composition will depend on various factors including the desired end use of the composition and the cured product thereof. However, the amount of ingredient (E) may range from 0.1 % to 10 % based on the combined weights of all ingredients in the composition.
  • Ingredient (F) is a filler.
  • the filler may comprise a reinforcing filler, an extending filler, a conductive filler, or a combination thereof.
  • the composition may optionally further comprise ingredient (fl), a reinforcing filler, which when present may be added in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, based on the weight of the composition.
  • suitable reinforcing fillers include reinforcing silica fillers such as fume silica, silica aerogel, silica xerogel, and precipitated silica. Fumed silicas are known in the art and commercially available; e.g. , fumed silica sold under the name CAB-O-SIL by Cabot Corporation of Massachusetts, U.S.A.
  • the composition may optionally further comprise ingredient (f2) an extending filler in an amount ranging from 0.1 % to 95 %, alternatively 1 % to 60 %, and alternatively 1 % to 20 %, based on the weight of the composition.
  • extending fillers include crushed quartz, aluminum oxide, magnesium oxide, calcium carbonate such as precipitated calcium carbonate, zinc oxide, talc, diatomaceous earth, iron oxide, clays, mica, chalk, titanium dioxide, zirconia, sand, carbon black, graphite, or a combination thereof.
  • Extending fillers are known in the art and commercially available; such as a ground silica sold under the name MIN-U-SIL by U.S. Silica of Berkeley Springs, WV.
  • Suitable precipitated calcium carbonates included Winnofil® SPM from Solvay and Ultrapflex® and Ultrapflex® 100 from SMI.
  • the composition may optionally further comprise ingredient (f3) a conductive filler.
  • Conductive fillers may be thermally conductive, electrically conductive, or both.
  • Conductive fillers are known in the art and are exemplified by metal particulates (such as aluminum, copper, gold, nickel, silver, and combinations thereof); such metals coated on nonconductive substrates; metal oxides (such as aluminum oxide, beryllium oxide, magnesium oxide, zinc oxide, and combinations thereof), meltable fillers (e.g. , solder), aluminum nitride, aluminum trihydrate, barium titanate, boron nitride, carbon fibers, diamond, graphite, magnesium hydroxide, onyx, silicon carbide, tungsten carbide, and a combination thereof.
  • fillers may be added to the composition, the type and amount depending on factors including the end use of the cured product of the composition.
  • Examples of such other fillers include magnetic particles such as ferrite; and dielectric particles such as fused glass microspheres, titania, and calcium carbonate.
  • the composition may optionally further comprise ingredient (G) a treating agent.
  • ingredient (G) a treating agent.
  • the amount of ingredient (G) will vary depending on factors such as the type of treating agent selected and the type and amount of particulates to be treated, and whether the particulates are treated before being added to the composition, or whether the particulates are treated in situ. However, ingredient (G) may be used in an amount ranging from 0.01 % to 20 %, alternatively 0.1 % to 15 %, and alternatively 0.5 % to 5 %, based on the weight of the composition.
  • Particulates such as the filler, the physical drying agent, certain flame retardants, certain pigments, and/or certain water release agents, when present, may optionally be surface treated with ingredient (G).
  • Ingredient (G) may comprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl- functional oligosiloxane such as a dimethyl siloxane or methyl phenyl siloxane, or a fatty acid.
  • fatty acids include stearates such as calcium stearate.
  • organosilicon filler treating agents that can be used as ingredient (G) include compositions normally used to treat silica fillers such as
  • organochlorosilanes organosiloxanes, organodisilazanes such as hexaalkyl disilazane, and organoalkoxysilanes such as C 6 H 13 Si(OCH 3 )3, C 8 H 17 Si(OC2H 5 ) 3 , CioH 2 iSi(OCH 3 )3, Ci2H 2 5Si(OCH 3 )3, C i 4 H 2 9Si(OC2H 5 )3, and C 6 H 5 CH2CH 2 Si(OCH3)3.
  • Other treating agents that can be used include alkylthiols, fatty acids, titanates, titanate coupling agents, zirconate coupling agents, and combinations thereof.
  • ingredient (G) may comprise an alkoxysilane having the formula: where subscript p may have a value ranging from 1 to 3, alternatively subscript p is 3.
  • Each R.13 is independently a monovalent organic group, such as a monovalent hydrocarbon group of 1 to 50 carbon atoms, alternatively 8 to 30 carbon atoms, alternatively 8 to 18 carbon atoms.
  • R.13 is exemplified by alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; and aromatic groups such as benzyl and phenylethyl.
  • R.13 may be saturated or unsaturated, and branched or unbranched.
  • R.13 may be saturated and unbranched.
  • Each R.14 is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
  • Ingredient (G) is exemplified by hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane,
  • Alkoxy-functional oligosiloxanes may also be used as treating agents.
  • suitable alkoxy-functional oligosiloxanes include those of the formula
  • subscript q is 1 , 2 or 3, alternatively
  • Each R!5 may be an alkyl group.
  • Each R!6 may be an unsaturated monovalent hydrocarbon group of 1 to 10 carbon atoms.
  • Each R!7 may be an unsaturated monovalent hydrocarbon group having at least 10 carbon atoms.
  • Certain particulates, such as metal fillers may be treated with alkyl thiols such as octadecyl mercaptan; fatty acids such as oleic acid and stearic acid; and a combination thereof.
  • alkyl thiols such as octadecyl mercaptan
  • fatty acids such as oleic acid and stearic acid
  • alkenyl functional polyorganosiloxanes include, but are not limited to:
  • I I I CH 2 CH-Si-(OSi) r -OSi-CH 3
  • subscript r has a value up to 1 ,500.
  • a polyorganosiloxane capable of hydrogen bonding is useful as a treating agent.
  • This strategy to treating surface of a filler takes advantage of multiple hydrogen bonds, either clustered or dispersed or both, as the means to tether the compatibilization moiety to the filler surface.
  • the polyorganosiloxane capable of hydrogen bonding has an average, per molecule, of at least one silicon-bonded group capable of hydrogen bonding.
  • the group may be selected from: an organic group having multiple hydroxyl functionalities or an organic group having at least one amino functional group.
  • the polyorganosiloxane capable of hydrogen bonding means that hydrogen bonding is the primary mode of attachment for the polyorganosiloxane to a filler.
  • the polyorganosiloxane may be incapable of forming covalent bonds with the filler.
  • the polyorganosiloxane may be free of condensable silyl groups e.g. , silicon bonded alkoxy groups, silazanes, and silanols.
  • the polyorganosiloxane capable of hydrogen bonding may be selected from the group consisting of a saccharide-siloxane polymer, an amino-functional polyorganosiloxane, and a combination thereof.
  • the polyorganosiloxane capable of hydrogen bonding may be a saccharide-siloxane polymer.
  • Ingredient (H) is a biocide.
  • the amount of ingredient (H) will vary depending on factors including the type of biocide selected and the benefit desired. However, the amount of ingredient (H) may range from greater than 0 % to 5 % based on the weight of all ingredients in the composition.
  • Ingredient (H) is exemplified by (hi) a fungicide, (h2) an herbicide, (h3) a pesticide, or a combination thereof.
  • Ingredient (hi) is a fungicide, for example, these include N-substituted
  • benzimidazole carbamate benzimidazolyl carbamate such as methyl 2- benzimidazolylcarbamate, ethyl 2-benzimidazolylcarbamate, isopropyl 2- benzimidazolylcarbamate, methyl N- ⁇ 2-[l-(N,N- dimethylcarbamoyl)benzimidazolyl] ⁇ carbamate, methyl N- ⁇ 2-[l-(N,N-dimethylcarbamoyl)- 6-methylbenzimidazolyl] ⁇ carbamate, methyl N- ⁇ 2-[l-(N,N-dimethylcarbamoyl)-5- methylbenzimidazolyl] ⁇ carbamate, methyl N- ⁇ 2-[l-(N-methylcarbamoyl)benzimidazolyl] ⁇ carbamate, methyl N- ⁇ 2-[l-(N-methylcarbamoyl)-6-methylbenzimidazolyl] ⁇ carbamate,
  • Ingredient (h2) is an herbicide
  • suitable herbicides include amide herbicides such as allidochlor N,N-diallyl-2-chloroacetamide; CDEA 2-chloro-N,N- diethylacetamide; etnipromid (/?5')-2-[5-(2,4-dichlorophenoxy)-2-nitrophenoxy]-N- ethylpropionamide; anilide herbicides such as cisanilide ds-2,5-dimethylpyrrolidine-l- carboxanilide; flufenacet 4'-fluoro-N-isopropyl-2-[5-(trifluoromethyl)-l,3,4-thiadiazol-2- yloxyjacetanilide; naproanilide (/?5')-a-2-naphthoxypropionanilide; arylalanine herbicides such as benzoylprop N-benzoyl-N-(
  • antibiotic herbicides such as bilanafos 4- [hydroxy (methyl)phosphinoyl]-L-homoalanyl-L- alanyl-L-alanine; benzoic acid herbicides such as chloramben 3-amino-2,5-dichlorobenzoic acid; 2,3,6-TBA 2,3,6-trichlorobenzoic acid; pyrimidinyloxybenzoic acid herbicides such as bispyribac 2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid; pyrimidinylthiobenzoic acid herbicides such as pyrithiobac 2-chloro-6-(4,6-dimethoxypyrimidin-2-ylthio)benzoic acid; phthalic acid herbicides such as chlorthal tetrachloroterephthalic acid; picolinic acid herbicides such as aminopyralid 4-amino-3,6-dichloropyridine-2-carboxylic acid;
  • quinolinecarboxylic acid herbicides such as quinclorac 3,7-dichloroquinoline-8-carboxylic acid
  • arsenical herbicides such as CMA calcium bis(hydrogen methylarsonate); MAMA ammonium hydrogen methylarsonate; sodium arsenite
  • benzoylcyclohexanedione herbicides such as mesotrione 2-(4-mesyl-2-nitrobenzoyl)cyclohexane-l ,3-dione
  • benzofuranyl alkylsulphonate herbicides such as benfuresate 2,3-dihydro-3,3-dimethylbenzofuran-5-yl ethanesulphonate
  • carbamate herbicides such as carboxazole methyl 5-3 ⁇ 4ri-butyl-l ,2-oxazol- 3-ylcarbamate
  • halogenated aliphatic herbicides such as dalapon 2,2-dichloropropionic acid; chloroacetic acid; imidazolinone herbicides such as imazapyr (/?5')-2-(4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl)nicotinic acid; inorganic herbicides such as disodium tetraborate
  • nitrile herbicides such as chloroxynil 3,5-dichloro-4- hydroxybenzonitrile; ioxynil 4-hydroxy-3,5-di-iodobenzonitrile; organophosphorus herbicides such as anilofos 5'-4-chloro-N-isopropylcarbaniloylmethyl O, O-dimethyl phosphorodithioate; glufosinate 4- [hydroxy (methyl)phosphinoyl]-DL-homoalanine; phenoxy herbicides such as clomeprop (/?5')-2-(2,4-dichloro-m-tolyloxy)propionanilide; fenteracol 2- (2,4,5-trichlorophenoxy)ethanol; phenoxyacetic herbicides such as MCPA (4-chloro-2- methylphenoxy)acetic acid; phenoxybutyric herbicides such as MCPB 4-(4-chloro-o- tolyl
  • chloro-N -isopropylpyrimidine-2,4-diamine quaternary ammonium herbicides such as diethamquat l, -bis(diethylcarbamoylmethyl)-4,4'-bipyridinium; paraquat 1 , 1 '-dimethyl- 4,4'-bipyridinium; thiocarbamate herbicides such as cycloate S-ethyl
  • thiocarbonate herbicides such as EXD 0, 0-diethyl dithiobis(thioformate); thiourea herbicides such as methiuron l ,l-dimethyl-3-m-tolyl-2-thiourea; triazine herbicides such as triaziflam (/?5')-N-[2-(3,5-dimethylphenoxy)-l-methylethyl]-6-(l-fluoro-l-methylethyl)-l ,3,5-triazine-
  • chlorotriazine herbicides such as cyprazine 6-chloro-N ⁇ -cyclopropyl-N ⁇ - isopropyl-l,3,5-triazine-2,4-diamine; propazine
  • methoxytriazine herbicides such as prometon N ,N -di-isopropyl-6-methoxy- l,3,5-triazine-2,4-diamine
  • methylthiotriazine herbicides such as cyanatryn 2-(4-ethylamino- 6-methylthio-l,3,5-triazin-2-ylamino)-2-methylpropionitrile
  • triazinone herbicides such as hexazinone 3-cyclohexyl-6-dimethylamino-l -methyl- 1, 3, 5-triazine-2,4(lH,3H)-dione
  • triazole herbicides such as epronaz N-ethyl-N-propyl-3-propylsulphonyl-lH-l,2,4-triazole-l- carboxamide
  • triazolone herbicides such as carfentrazone (/?5')-2-chloro
  • Ingredient (h3) is a pesticide.
  • Suitable pesticides are exemplified by atrazine, diazinon, and chlorpyrifos.
  • pesticide includes insect repellents such as ⁇ , ⁇ -diethyl-meta-toluamide and pyrethroids such as pyrethrin.
  • Ingredient (h4) is an antimicrobial agent. Suitable antimicrobials are commercially available, such as DOW CORNING® 5700 and DOW CORNING® 5772, which are from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • ingredient (H) may comprise a boron containing material, e.g. , boric anhydride, borax, or disodium octaborate tetrahydrate; which may function as a pesticide, fungicide, and/or flame retardant.
  • a boron containing material e.g. , boric anhydride, borax, or disodium octaborate tetrahydrate; which may function as a pesticide, fungicide, and/or flame retardant.
  • Ingredient (J) is a flame retardant.
  • Suitable flame retardants may include, for example, carbon black, hydrated aluminum hydroxide, and silicates such as wollastonite, platinum and platinum compounds.
  • the flame retardant may be selected from halogen based flame-retardants such as decabromodiphenyloxide, octabromordiphenyl oxide, hexabromocyclododecane, decabromobiphenyl oxide, diphenyoxybenzene, ethylene bis- tetrabromophthalmide, pentabromoethyl benzene, pentabromobenzyl acrylate,
  • tribromophenyl maleic imide tetrabromobisphenyl A, bis-(tribromophenoxy) ethane, bis- (pentabromophenoxy) ethane, polydibomophenylene oxide, tribromophenylallyl ether, bis- dibromopropyl ether, tetrabromophthalic anhydride, dibromoneopentyl gycol, dibromoethyl dibromocyclohexane, pentabromodiphenyl oxide, tribromostyrene,
  • the flame retardant may be selected from phosphorus based flame-retardants such as (2,3- dibromopropyl)-phosphate, phosphorus, cyclic phosphates, triaryl phosphate, bis- melaminium pentate, pentaerythritol bicyclic phosphate, dimethyl methyl phosphate, phosphine oxide diol, triphenyl phosphate, tris- (2-chloroethyl) phosphate, phosphate esters such as tricreyl, trixylenyl, isodecyl diphenyl, ethylhexyl diphenyl, phosphate salts of various amines such as ammonium phosphate, trioctyl, tributyl or tris-butoxyethyl phosphate ester.
  • phosphorus based flame-retardants such as (2,3- dibromopropyl)-phosphate, phosphorus, cycl
  • flame retardants may include tetraalkyl lead compounds such as tetraethyl lead, iron pentacarbonyl, manganese methyl cyclopentadienyl tricarbonyl, melamine and derivatives such as melamine salts, guanidine, dicyandiamide, ammonium sulphamate, alumina trihydrate, and magnesium hydroxide alumina trihydrate.
  • tetraalkyl lead compounds such as tetraethyl lead, iron pentacarbonyl, manganese methyl cyclopentadienyl tricarbonyl, melamine and derivatives such as melamine salts, guanidine, dicyandiamide, ammonium sulphamate, alumina trihydrate, and magnesium hydroxide alumina trihydrate.
  • the amount of flame retardant will vary depending on factors such as the flame retardant selected and whether solvent is present. However, the amount of flame retardant in the composition may range from greater than 0 % to 10 % based on the combined weight of all ingredients in the composition.
  • Ingredient (K) is a surface modifier.
  • Suitable surface modifiers are exemplified by (kl) an adhesion promoter or (k2) a release agent.
  • Suitable adhesion promoters for ingredient (kl) may comprise a transition metal chelate, a hydrocarbonoxysilane such as an
  • alkoxysilane a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane, an aminofunctional silane, or a combination thereof.
  • Adhesion promoters are known in the
  • 24 25 26 24 art may comprise silanes having the formula R u Si(OR )4_(t + u ) where each R
  • the adhesion promoter may comprise a partial condensate of the above silane.
  • the adhesion promoter may comprise a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.
  • the adhesion promoter may comprise an unsaturated or epoxy- functional compound.
  • the adhesion promoter may comprise an unsaturated or epoxy- functional alkoxysilane.
  • the functional alkoxysilane can have the formula where subscript v is 1, 2, or 3, alternatively subscript v is 1.
  • Each R 27 is independently a monovalent organic group with the proviso that at least one R 27 is an unsaturated organic group or an epoxy-functional organic group.
  • Epoxy-functional organic groups for R ⁇ 7 are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl.
  • Unsaturated organic groups for R ⁇ 7 are exemplified by 3-methacryloyloxypropyl, 3- acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl.
  • Each R ⁇ 8 is independently a saturated hydrocarbon group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms.
  • R ⁇ 8 is exemplified by methyl, ethyl, propyl, and butyl.
  • Examples of suitable epoxy-functional alkoxysilanes include 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
  • vinyltrimethoxysilane allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3- methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyl trimethoxysilane, 3- acryloyloxypropyl triethoxysilane, and combinations thereof.
  • the adhesion promoter may comprise an epoxy-functional siloxane such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy- functional alkoxysilane, as described above, or a physical blend of the hydroxy-terminated polyorganosiloxane with the epoxy-functional alkoxysilane.
  • the adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane.
  • the adhesion promoter is exemplified by a mixture of 3- glycidoxypropyltrimethoxysilane and a reaction product of hydroxy-terminated
  • methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane or a mixture of 3- glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated
  • the adhesion promoter may comprise an aminofunctional silane, such as an aminofunctional alkoxysilane exemplified by H2N(CH2)2Si(OCH3)3,
  • the adhesion promoter may comprise a transition metal chelate.
  • Suitable transition metal chelates include titanates, zirconates such as zirconium
  • acetylacetonate aluminum chelates such as aluminum acetylacetonate, and combinations thereof.
  • Ingredient (k2) is a release agent.
  • Suitable release agents are exemplified by fluorinated compounds, such as fluoro-functional silicones, or fluoro-functional organic compounds.
  • the surface modifier for ingredient (K) may be used to change the appearance of the surface of a reaction product of the composition.
  • surface modifier may be used to increase gloss of the surface of a reaction product of the
  • Such a surface modifier may comprise a polydiorganosiloxane with alkyl and aryl groups.
  • DOW CORNING® 550 Fluid is a trimethylsiloxy-terminated poly(dimethyl/methylphenyl)siloxane with a viscosity of 125 cSt that is commercially available from Dow Corning Corporation.
  • ingredient (K) may be a natural oil obtained from a plant or animal source, such as linseed oil, tung oil, soybean oil, castor oil, fish oil, hempseed oil, cottonseed oil, oiticica oil, and rapeseed oil.
  • ingredient (K) depends on various factors including the type of surface modifier selected as ingredient (K) and the end use of the composition and its reaction product. However, ingredient (K), when present, may be added to the composition in an amount ranging from 0.01 to 50 weight parts based on the weight of the composition, alternatively 0.01 to 10 weight parts, and alternatively 0.01 to 5 weight parts. Ingredient (K) may be one adhesion promoter. Alternatively, ingredient (K) may comprise two or more different surface modifiers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
  • Chain lengtheners may include difunctional silanes and difunctional siloxanes, which extend the length of polyorganosiloxane chains before crosslinking occurs. Chain lengtheners may be used to reduce the modulus of elongation of the cured product. Chain lengtheners and crosslinkers compete in their reactions with the hydrolyzable substituents in ingredient (B). To achieve noticeable chain extension, the difunctional silane has substantially higher reactivity than the trifunctional crosslinker with which it is used.
  • Suitable chain lengtheners include diamidosilanes such as dialkyldiacetamidosilanes or alkenylalkyldiacetamidosilanes, particularly methylvinyldi(N-methylacetamido)silane, or dimethyldi(N-methylacetamido)silane, diacetoxysilanes such as dialkyldiacetoxysilanes or alkylalkenyldiacetoxysilanes, diaminosilanes such as dialkyldiaminosilanes or
  • alkylalkenyldiaminosilanes dialkoxysilanes such as dimethyldimethoxysilane
  • dimethyldiethoxysilane and a-aminoalkyldialkoxyalkylsilanes polydialkylsiloxanes having a degree of polymerization of from 2 to 25 and having an average per molecule of at least two hydrolyzable groups, such as acetamido or acetoxy or amino or alkoxy or amido or ketoximo substituents, and diketoximinosilanes such as dialkylkdiketoximinosilanes and
  • Ingredient (L) may be one chain lengthener.
  • ingredient (L) may comprise two or more different chain lengtheners that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence
  • Ingredient (M) is and endblocker comprising an M unit, i.e. , a siloxane unit of
  • each R independently represents a monovalent organic group unreactive ingredient (B), such as a monovalent hydrocarbon group.
  • Ingredient (M) may comprise polyorganosiloxanes endblocked on one terminal end by a triorganosilyl group, e.g. , (CH3)3SiO-, and on the other end by a hydroxyl group.
  • Ingredient (M) may be a polydiorganosiloxane such as a polydimethylsiloxane.
  • the polydiorganosiloxanes having both hydroxyl end groups and triorganosilyl end groups may have more than 50 %, alternatively more than 75 %, of the total end groups as hydroxyl groups.
  • the amount of triorganosilyl group in the polydimethylsiloxane may be used to regulate the modulus of the reaction product prepared by condensation reaction of the composition. Without wishing to be bound by theory, it is thought that higher concentrations of triorganosilyl end groups may provide a lower modulus in certain cured products.
  • Ingredient (M) may be one endblocker. Alternatively, ingredient (M) may comprise two or more different endblockers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
  • Ingredient (N) is a non-reactive, elastomeric, organic polymer, i.e. , an elastomeric organic polymer that does not react with ingredient (B).
  • Ingredient (N) is compatible with ingredient (B), i.e. , ingredient (N) does not form a two-phase system with ingredient (B).
  • Ingredient (N) may have low gas and moisture permeability.
  • Ingredient (N) may have Mn ranging from 30,000 to 75,000.
  • ingredient (N) may be a blend of a higher molecular weight, non-reactive, elastomeric, organic polymer with a lower molecular weight, non-reactive, elastomeric, organic polymer.
  • the higher molecular weight polymer may have Mn ranging from 100,000 to 600,000 and the lower molecular weight polymer may have Mn ranging from 900 to 10,000, alternatively 900 to 3,000.
  • the value for the lower end of the range for Mn may be selected such that ingredient (N) has compatibility with ingredient (B) and the other ingredients of the composition.
  • Ingredient (N) may comprise a polyisobutylene.
  • Polyisobutylenes are known in the art and are commercially available. Examples suitable for use as ingredient (N) include polyisobutylenes marketed under the trademark OPPANOL® by BASF Corporation of Germany. Such polyisobutylenes are summarized in the table below.
  • polyisobutylenes include different Parleam grades such as highest molecular weight hydrogenated polyisobutene PARLEAM® SV (POLYSYNLANE SV) from NOF CORPORATION Functional Chemicals & Polymers Div., Yebisu Garden Place Tower , 20-3 Ebisu 4-chome, Shibuya-ku, Tokyo 150-6019, Japan (Kinematic Viscosity (98.9°C) 4700).
  • PARLEAM® SV POLYSYNLANE SV
  • NOF CORPORATION Functional Chemicals & Polymers Div. Yebisu Garden Place Tower , 20-3 Ebisu 4-chome, Shibuya-ku, Tokyo 150-6019, Japan (Kinematic Viscosity (98.9°C) 4700).
  • polyisobutylenes are commercially available from ExxonMobil Chemical Co. of Baytown, Texas, U.S.A. and include polyisobutylenes marketed under the trademark VISTANEX®, such as MML-80, MML-100, MML-120, and MML-140.
  • VISTANEX® polyisobutylenes are paraffinic hydrocarbon polymers, composed of long, straight-chain macromolecules containing only chain-end olefinic bonds.
  • polyisobutylenes have viscosity average molecular weight ranging from 70,000 to 90,000.
  • Lower molecular weight polyisobutylenes include VISTANEX® LM, such as LM-MS (viscosity average molecular weight ranging from 8,700 to 10,000 also made by ExxonMobil Chemical Co.) and VISTANEX LM-MH (viscosity average molecular weight of 10,000 to 11,700) as well as Soltex PB-24 (Mn 950) and Indopol® H-100 (Mn 910) and Indopol® H- 1200 (Mn 2100) from Amoco.
  • Other polyisobutylenes are marketed under the trademarks NAPVIS® and HYVIS® by BP Chemicals of London, England. These polyisobutylenes include NAPVIS® 200, D10, and DE3; and HYVIS® 200.
  • the NAP VIS® polyisobutylenes may have Mn ranging from 900 to 1300.
  • ingredient (N) may comprise butyl rubber.
  • ingredient (N) may comprise a styrene-ethylene/butylene-styrene (SEBS) block copolymer, a styrene- ethylene/propylene-styrene (SEPS) block copolymer, or a combination thereof.
  • SEBS and SEPS block copolymers are known in the art and are commercially available as Kraton® G polymers from Kraton Polymers U.S. LLC of Houston, Texas, U.S.A., and as Septon polymers from Kuraray America, Inc., New York, NY, U.S.A.
  • ingredient (N) may comprise a polyolefin plastomer.
  • Polyolefin plastomers are known in the art and are commercially available as AFFINITY® GA 1900 and AFFINITY® GA 1950 from Dow Chemical Company, Elastomers & Specialty Products Division, Midland, Michigan, U.S.A.
  • the amount of ingredient (N) may range from 0 parts to 50 parts, alternatively 10 parts to 40 parts, and alternatively 5 parts to 35 parts, based on the weight of the composition.
  • Ingredient (N) may be one non-reactive, elastomeric, organic polymer.
  • ingredient (N) may comprise two or more non-reactive, elastomeric, organic polymers that differ in at least one of the following properties: structure, viscosity, average molecular weight, polymer units, and sequence.
  • ingredient (N) may be added to the composition when ingredient (B) comprises a base polymer with an organic polymer backbone.
  • Ingredient (O) is an anti-aging additive.
  • the anti-aging additive may comprise an antioxidant, a UV absorber, a UV stabilizer, a heat stabilizer, or a combination thereof.
  • Suitable antioxidants are known in the art and are commercially available. Suitable antioxidants include phenolic antioxidants and combinations of phenolic antioxidants with stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols. Alternatively, the stabilizer may be a sterically hindered amine such as tetramethyl-piperidine derivatives. Suitable phenolic antioxidants include vitamin E and IRGANOX® 1010 from Ciba Specialty Chemicals, U.S.A. IRGANOX® 1010 comprises pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate).
  • UV absorbers examples include phenol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-, branched and linear (TINUVIN® 571).
  • UV stabilizers include bis(l ,2,2,6,6-pentamethyl-4- piperidyl) sebacate; methyl l,2,2,6,6-pentamethyl-4-piperidyl/sebacate; and a combination thereof (TINUVIN® 272).
  • TINUVIN® 272 examples include bis(l ,2,2,6,6-pentamethyl-4- piperidyl) sebacate; methyl l,2,2,6,6-pentamethyl-4-piperidyl/sebacate; and a combination thereof (TINUVIN® 272).
  • TINUVIN® additives such as TINUVIN® 765 are commercially available from Ciba Specialty Chemicals of Tarrytown, NY, U.S.A.
  • UV and light stabilizers are commercially available, and are exemplified by LowLite from Chemtura, OnCap from Poly One, and Light Stabilizer 210 from E. I. du Pont de Nemours and Company of Delaware, U.S.A.
  • Oligomeric (higher molecular weight) stabilizers may alternatively be used, for example, to minimize potential for migration of the stabilizer out of the composition or the cured product thereof.
  • An example of an oligomeric antioxidant stabilizer specifically, hindered amine light stabilizer (HALS)
  • HALS hindered amine light stabilizer
  • Heat stabilizers may include iron oxides and carbon blacks, iron carboxylate salts, cerium hydrate, barium zirconate, cerium and zirconium octoates, and porphyrins.
  • the amount of ingredient (O) depends on various factors including the specific anti- aging additive selected and the anti-aging benefit desired. However, the amount of ingredient (O) may range from 0 to 5 weight %, alternatively 0.1 % to 4 %, and alternatively 0.5 % to 3 %, based on the weight of the composition. Ingredient (O) may be one anti-aging additive. Alternatively, ingredient (O) may comprise two or more different anti-aging additives.
  • Ingredient (P) is a water release agent that releases water over an application temperature range.
  • Ingredient (P) is selected such that ingredient (P) contains an amount of water sufficient to partially or fully react the composition and such that ingredient (P) releases the sufficient amount of water when exposed for a sufficient amount of time to a use temperature (i.e. , a temperature at which the composition is used).
  • ingredient (P) binds the water sufficiently to prevent too much water from being released during the method for making the composition and during storage of the composition.
  • ingredient (P) binds the water sufficiently during compounding of the composition such that sufficient water is available for condensation reaction of the composition during or after the application process in which the composition is used.
  • This "controlled release” property also may provide the benefit of ensuring that not too much water is released too rapidly during the application process, since this may cause bubbling or voiding in the reaction product formed by condensation reaction of the composition.
  • Precipitated calcium carbonate may be used as ingredient (P) when the application temperature ranges from 80 °C to 120 °C, alternatively 90 °C to 110 °C, and alternatively 90 °C to 100 °C.
  • the ingredients may be compounded at a temperature 20 °C to 30 °C above the application temperature range for a short amount of time. Therefore, ingredient (P) is selected to ensure that not all of the water content is released during compounding, however ingredient (P) releases a sufficient amount of water for condensation reaction of the composition when exposed to the application temperature range for a sufficient period of time.
  • water release agents are exemplified by metal salt hydrates, hydrated molecular sieves, and precipitated calcium carbonate, which is available from Solvay under the trademark WINNOFIL® SPM.
  • the water release agent selected will depend on various factors including the other ingredients selected for the composition, including catalyst type and amount; and the process conditions during compounding, packaging, and application. In a twin-screw compounder, residence time may be less than a few minutes, typically less than 1 to 2 minutes. The ingredients are heated rapidly because the surface area/volume ratio in the barrels and along the screw is high and heat is induced by shearing the ingredients.
  • a water release agent may be added to the composition, for example, when the base polymer has low water permeability (e.g. , when the base polymer has an organic polymer backbone) and/or the amount of ingredient (P) in the composition depends on various factors including the selection of ingredients (A), (B) and (C) and whether any additional ingredients are present, however the amount of ingredient (P) may range from 5 to 30 parts based on the weight of the composition.
  • the amount of ingredient (P) may range from 5 to 30 parts based on the weight of the composition.
  • By-products such as alcohols and/or water left in the composition may be bound by a drying agent, thereby allowing the condensation reaction (which is an equilibrium reaction) to proceed toward completion.
  • Ingredient (Q) is a pigment.
  • the term 'pigment' includes any ingredient used to impart color to a reaction product of a composition described herein.
  • the amount of pigment depends on various factors including the type of pigment selected and the desired degree of coloration of the reaction product.
  • the composition may comprise 0 to 20 %, alternatively 0.001 % to 5 %, of a pigment based on the weight of all ingredients in the composition.
  • suitable pigments include indigo, titanium dioxide Stan-Tone 50SP01 Green (which is commercially available from PolyOne) and carbon black.
  • carbon black include Shawinigan Acetylene black, which is commercially available from Chevron Phillips Chemical Company LP; SUPERJET® Carbon Black (LB-1011) supplied by Elementis Pigments Inc., of Fairview Heights, IL U.S.A.; SR 511 supplied by Sid Richardson Carbon Co, of Akron, OH U.S.A.; and N330, N550, N762, N990 (from Degussa Engineered Carbons of Parsippany, NJ, U.S.A.).
  • the composition may optionally further comprise up to 5 %, alternatively 1 % to 2 % based on the weight of the composition of ingredient (R) a rheological additive for modifying rheology of the composition.
  • Rheological additives are known in the art and are commercially available. Examples include poly amides, Poly vest, which is commercially available from Evonk, Disparlon from King Industries, Kevlar Fibre Pulp from Du Pont, Rheospan from Nanocor, and Ircogel from Lubrizol.
  • Other suitable rheological additives include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate and barium stearate, and combinations thereof.
  • ingredient (R) may comprise a microcrystalline wax that is a solid at 25 °C (wax).
  • the melting point may be selected such that the wax has a melting point at the low end of the desired application temperature range.
  • ingredient (R) acts as a process aid that improves flow properties while allowing rapid green strength development (i.e. , a strong increase in viscosity, corresponding to increase in the load carrying capability of a seal prepared from the composition, with a temperature drop) upon cooling the composition a few degrees, for example, after the composition is applied to a substrate.
  • incorporation of wax may also facilitate incorporation of fillers, compounding and de-airing (during production of the composition), and mixing (static or dynamic mixing during application of parts of a multiple-part composition).
  • the wax when molten, serves as a process aid, substantially easing the incorporation of filler in the composition during compounding, the compounding process itself, as well as in during a de-airing step, if used.
  • the wax with a melt temperature below 100 °C, may facilitate mixing of the parts of a multiple part composition before application, even in a simple static mixer.
  • the wax may also facilitate application of the composition at temperatures ranging from 80 °C to 110 °C, alternatively 90 °C to 100 °C with good rheology.
  • Waxes suitable for use as ingredient (R) may be non-polar hydrocarbons.
  • the waxes may have branched structures, cyclic structures, or combinations thereof.
  • petroleum microcrystalline waxes are available from Strahl & Pitsch, Inc., of West Arabic, NY, U.S.A.
  • SP 96 melting point ranging from 62 °C to 69 °C
  • SP 18 melting point ranging from 73 °C to 80 °C
  • SP 19 melting point ranging from 76 °C to 83 °C
  • SP 26 melting point ranging from 76 °C to 83 °C
  • SP 60 melting point ranging from 79 °C to 85 °C
  • SP 617 melting point ranging from 88 °C to 93 °C
  • SP 89 melting point ranging from 90 °C to 95 °C
  • SP 624 melting point ranging from 90 °C to 95 °C
  • the amount of ingredient (R) depends on various factors including the specific rheological additive selected and the selections of the other ingredients of the composition. However, the amount of ingredient (R) may range from 0 parts to 20 parts, alternatively 1 parts to 15 parts, and alternatively 1 part to 5 parts based on the weight of the composition. Ingredient (R) may be one rheological additive. Alternatively, ingredient (R) may comprise two or more different rheological additives.
  • Solvent may be used in the composition. Solvent may facilitate flow of the composition and introduction of certain ingredients, such as silicone resin. Solvents used herein are those that help fluidize the ingredients of the composition but essentially do not react with any of these ingredients. Solvent may be selected based on solubility the ingredients in the composition and volatility. The solubility refers to the solvent being sufficient to dissolve and/or disperse ingredients of the composition. Volatility refers to vapor pressure of the solvent. If the solvent is too volatile (having too high vapor pressure) bubbles may form in the composition at the application temperature, and the bubbles may cause cracks or otherwise weaken or detrimentally affect properties of the cured product. However, if the solvent is not volatile enough (too low vapor pressure) the solvent may remain as a plasticizer in the reaction product of the composition, or the amount of time for the reaction product to develop physical properties may be longer than desired.
  • solubility refers to the solvent being sufficient to dissolve and/or disperse ingredients of the composition. Volatility refers to vapor pressure of the solvent
  • Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane and other low molecular weight polyorganosiloxanes, such as 0.5 to 1.5 centiStoke (cSt) Dow Corning® 200 Fluids and DOW CORNING® OS FLUIDS, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • suitable vapor pressures such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane and other low molecular weight polyorganosiloxanes, such as 0.5 to 1.5 centiStoke (cSt) Dow Corning® 200 Fluids and DOW CORNING® OS FLUIDS, which are commercially available from Dow Corning Corporation of Midland, Michigan, U.S.A.
  • the solvent may be an organic solvent.
  • the organic solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether, a halogenated hydrocarbon such as dichloromethane, 1,1 ,1-trichloroethane or methylene chloride; chloroform; dimethyl sulfoxide
  • the amount of solvent will depend on various factors including the type of solvent selected and the amount and type of other ingredients selected for the composition. However, the amount of solvent may range from 1 % to 99%, alternatively 2 % to 50 %, based on the weight of the composition.
  • the composition may optionally further comprise ingredient (T) a tackifying agent.
  • the tackifying agent may comprise an aliphatic hydrocarbon resin such as a hydrogenated polyolefin having 6 to 20 carbon atoms, a hydrogenated terpene resin, a rosin ester, a hydrogenated rosin glycerol ester, or a combination thereof. Tackifying agents are commercially available.
  • Aliphatic hydrocarbon resins are exemplified by ESCOREZ 1102, 1304, 1310, 1315, and 5600 from Exxon Chemical and Eastotac resins from Eastman, such as Eastotac H-100 having a ring and ball softening point of 100 °C, Eastotac H-l 15E having a ring and ball softening point of 115 °C, and Eastotac H-130L having a ring and ball softening point of 130 °C.
  • Hydrogenated terpene resins are exemplified by Arkon P 100 from Arakawa Chemicals and Wingtack 95 from Goodyear.
  • Hydrogenated rosin glycerol esters are exemplified by Staybelite Ester 10 and Foral from Hercules. Examples of commercially available polyterpenes include Piccolyte A125 from Hercules. Examples of
  • aliphatic/aromatic or cycloaliphatic/aromatic resins include ECR 149B or ECR 179A from
  • a solid tackifying agent i. e. , a tackifying agent having a ring and ball softening point above 25 °C
  • Suitable tackifying agents include any compatible resins or mixtures thereof such as (1) natural or modified rosins such, for example, as gum rosin, wood rosin, tall-oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; (2) glycerol and pentaerythritol esters of natural or modified rosins, such, for example as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic-modified pentaerythritol ester of rosin; (3) copoly
  • polyterpene resins having a softening point as determined by ASTM method E28,58T, ranging from 60 °C to 150 °C; the latter polyterpene resins generally resulting from the polymerization of terpene hydrocarbons, such as the bicyclic monoterpene known as pinene, in the presence of Friedel- Crafts catalysts at moderately low temperatures; also included are the hydrogenated polyterpene resins; (5) phenolic modified terpene resins and hydrogenated derivatives thereof, for example, as the resin product resulting from the condensation, in an acidic medium, of a bicyclic terpene and phenol; (6) aliphatic petroleum hydrocarbon resins having a ring and ball softening point ranging from 60 °C to 135 °C; the latter resins resulting from the polymerization of monomers consisting of primarily of olefins
  • ingredients for the composition described above there may be overlap between types of ingredients because certain ingredients described herein may have more than one function.
  • certain alkoxysilanes may be useful as filler treating agents and as adhesion promoters
  • certain fatty acid esters may be useful as plasticizers and may also be useful as filler treating agents
  • carbon black may be useful as a pigment, a flame retardant, and/or a filler
  • nonreactive polydiorganosiloxanes such as polydimethylsiloxanes may be useful as extenders and as solvents.
  • compositions such that the reaction product of the composition has a desired form, such as a gum, a gel, or a rubber.
  • composition described above may be prepared as a one part composition, for example, by combining all ingredients by any convenient means, such as mixing.
  • a one-part composition may be made by optionally combining (e.g. , premixing) the base polymer (B) and an extender (E) and mixing the resulting extended base polymer with all or part of the filler (F), and mixing this with a pre-mix comprising the crosslinker (C) and ingredient (A).
  • Other additives such as (O) the anti-aging additive and (Q) the pigment may be added to the mixture at any desired stage.
  • a final mixing step may be performed under substantially anhydrous conditions, and the resulting compositions are generally stored under substantially anhydrous conditions, for example in sealed containers, until ready for use.
  • the composition may be prepared as a multiple part (e.g. , 2 part) composition when a crosslinker is present.
  • a two part curable composition may be prepared by combining ingredients comprising (B) and (C) to form a first (curing agent) part by any convenient means such as mixing.
  • a second (base) part may be prepared by combining ingredients comprising (A) and (B) by any convenient means such as mixing.
  • the ingredients may be combined at ambient or elevated temperature and under ambient or anhydrous conditions, depending on various factors including whether a one part or multiple part composition is selected.
  • the base part and curing agent part may be combined by any convenient means, such as mixing, shortly before use.
  • the base part and curing agent part may be combined in relative amounts of base: curing agent ranging from 1 : 1 to 10: 1.
  • the equipment used for mixing the ingredients is not specifically restricted.
  • suitable mixing equipment may be selected by one of ordinary skill in the art depending on the type and amount of each ingredient selected.
  • agitated batch kettles may be used for relatively low viscosity compositions, such as compositions that will react to form gums or gels.
  • continuous compounding equipment e.g. , extruders such as twin screw extruders, may be used for more viscous compositions and compositions containing relatively high amounts of particulates.
  • extruders such as twin screw extruders
  • Exemplary methods that can be used to the compositions described herein include those disclosed in, for example, U.S. Patent Publications US 2009/0291238 and US 2008/0300358.
  • compositions made as described above may be stable when the stored in containers that protect the compositions from exposure to moisture, but these compositions may react via condensation reaction when exposed to atmospheric moisture.
  • the composition may cure to form a cured product when moisture is released from a water release agent.
  • compositions prepared as described above, and the reaction products thereof have various uses.
  • the ingredients described above may be used to prepare various types of composition comprising ingredients (A) and (B).
  • the composition may further comprise one or more of the additional ingredients described above, depending on the type of composition and the desired end use of the composition and/or the reaction product of the composition.
  • the ingredients and methods described above may be used for chain extension processes to increase viscosity of the base polymer and/or form a gum, for example, when the base polymer has an average of one to two hydrolyzable groups per molecule.
  • the ingredients and methods described above may be used to formulate curable compositions, for example, when the base polymer has two or more hydrolyzable groups per molecule and/or a crosslinker is present in the composition.
  • the compositions described herein may be reacted by condensation reaction by exposure to moisture.
  • the compositions may react via condensation reaction when exposed to atmospheric moisture.
  • the composition react moisture is released from a water release agent, when a water release agent is present.
  • the skin-over-time a measure of cure rate, is defined as the time in minutes required for curing material to form a non-tacky surface film by finger tip contact. Skin-over time represents the time within an end-user can tool a sealant joint.
  • Tack Free Time a measure of cure rate, was defined as the time in minutes required for a curing composition to form a non-tacky surface film by polyethylene contact. This method used polyethylene film contact to determine the non-tacky characteristics of a sealant. Tack-free time reflects the time needed for the surface of a product prepared by curing a composition to no longer pick-up dirt.
  • test panels were prepared as described below and touched with a gloved finger (disposable nitrile gloves) - the glove should be pulled toward the skin.
  • a gloved finger disosable nitrile gloves
  • an assessment of the test panels' (Q-panel) stickiness or tackiness was made. If no stickiness or tackiness was observed then the composition on the panel had cured, and the time taken from drawdown to tack free stage was recorded as the samples 'tack free time'.
  • Test panels that exhibited no cure after 4 days are labeled 'No Cure' . Any cure time beyond 4 days was not recorded.
  • the appearance of the test panel was also recorded, as well as the appearance and viscosity of the sample within the jar beyond two days. This data illustrates the compatibility and pot life of the samples and records any separation of materials, gelling, or discoloration.
  • Ingredient (B l) was a silanol terminated polydimethylsiloxane having a viscosity of 4000 cSt.
  • Ingredient (B2) was a methylmethoxysiloxane with methylsilsesquioxane resin having a DP of 15 and a Mw of 1,200, which was commercially available as DOW
  • Ingredient (B3) was a silanol terminated polydimethylsiloxane having a viscosity of 41 cSt.
  • Ingredient (CI) was methyltrimethoxysilane (MTM).
  • Ingredient (C2) was methyltriacetoxysilane (MTA).
  • Ingredient (C3) was methylethylketoxime silane (MTO).
  • Ingredient (C4) was a mixture of 50 % ethyltriacetoxysilane, 47%
  • TNBT refers to tetra-n- butyl titanate.
  • TNBT and DBTDL were used as positive controls to prepare comparative examples.
  • a catalyst, a crosslinker, and a base polymer were compounded together using the following method.
  • a 100 ml glass jar was used to mix all materials and provide safe storage for all samples.
  • a base polymer was added in an amount of 25 g to the jar followed by the crosslinker in an amount of 1.8 g or 0.5 g.
  • the crosslinker was added, the contents of the jar were mixed thoroughly by hand using a spatula for 30 seconds.
  • the catalyst was added to the jar and thoroughly mixed into the sample for 30 seconds or until the catalyst was uniformly mixed as much as possible.
  • drawdown of the sample was performed by adding a composition to the Q panel and passing a drawdown bar across the panel over the composition to form an even coating of the composition on the Q panel.
  • the drawdown was performed using a 100 ⁇ gap from the drawdown bar. Tack free time was measured according to the method of Reference Example 2.
  • a catalyst was added to 10 g of a resinous base polymer in a 14 ml glass snap top vial. The amount of catalyst was 0.1 g. The top was fastened, and the vial was shaken vigorously until mixed. The resulting solution was left undisturbed for 30 minutes, at which point a drawdown of the sample was performed as described in Reference Example 3.
  • Samples were prepared according to the method of Reference Example 3 using Ingredient (B l) a silanol terminated polydimethylsiloxane having a viscosity of 4000 cSt as the base polymer and 1.8 g of ingredient (CI) methyltrimethoxysilane as the crosslinker.
  • the catalysts shown below in the table were added as ingredient (A) in amounts of 0.1 %, 1.0 %, and 5.0 %.
  • Phospholan PE65 - 1 % No Cure forms a rubbery layer but is still sticky on its surface.
  • Example 1 showed that in this alkoxy curable polydimethylsiloxane composition, with the exception of tributylphosphate and tributylmethylammonium phosphate, all of the catalysts tested could cure the composition at various cure times and catalyst loadings.
  • DOW CORNING® 4-6085 appeared to catalyze slower cure than the phosphate esters, such as Nacure 4054.
  • DOW CORNING® 4-6085 had higher solids content and acid number, so more acid catalyst was present. Without wishing to be bound by theory, it was thought that because more haze was seen at high concentrations with the DOW
  • CORNING® 4-6085 there may have been incompatibility with the base polymer at high catalyst loadings of DOW CORNING® 4-6085 in the composition prepared in this example 2, however, DOW CORNING® 4-6085 was still capable of catalyzing condensation reaction in this composition.
  • Tristrimethylsilylphosphate catalyzed faster cure than DOW CORNING® 4-6085 under the conditions of Example 1. Without wishing to be bound by theory, it was thought that this was due to tristrimethylsilylphosphate being triacidic rather than diacidic on hydrolysis. Compatibility of tristrimethylsilylphosphate and DOW CORNING® 4-6085 might seem to be better at most catalysts loadings with cured films being clear and glossy, although DOW CORNING® 4-6085 showed slightly hazy films at 5 % catalyst loading in the composition of Example 1.
  • DOW CORNING® 4-6085 - 0.1 % increase Clear, no residues.
  • Phospholan PE65 - 0.1 % increase cloudy, no residue.
  • Phospholan PE 169 - 1 % increase cloudy, no residue.
  • Tris(trimethylsilyl)phosphate - 0.1 % increase Clear, no residues.
  • Tris(trimethylsilyl)phosphate - 1 % none Clear, no residues.
  • This example shows that DOW CORNING 4-6085 is sufficiently compatible with the base polymer and crosslinker of this Example 1 to be formulated into a composition containing a silanol terminated polydiorganosiloxane base polymer and a methoxysilane crosslinker. .
  • Samples were prepared according to the method of Reference Example 3 using Ingredient (B l) a silanol terminated polydimethylsiloxane having a viscosity of 4000 cSt as the base polymer and 0.5 g of ingredient (CI) methyltrimethoxysilane as the crosslinker.
  • the catalysts shown below in the table were added as ingredient (A) in amounts of 0.1 %, 1.0 %, and 5.0 %.
  • Example 2 all the compositions showed longer cure times than in Example 1. Higher MTM levels in Example 1 seemed to allow cure with lower catalyst levels. Of the compositions that cured, all of them had better or equivalent cure times than the control containing TNBT at 1 % and 5 % catalyst loading, but were worse at 0.1 % catalyst loading under the conditions of Example 2. Without wishing to be bound by theory, it was thought that poor performance at the low catalyst loading may have been due to loss of the crosslinker through evaporation before it could react with the base polymer and crosslink the
  • Example 2 Overall the appearance of the compositions in Example 2 were hazier than the compositions in Example 1 after storage for 2 days, as shown in the table below. More haze was seen at higher catalyst loading.
  • the least hazy compositions in Example 3 contained TNBT (the control), Nacure 4054, Nacure XC-9207, trimethylsilyl phosphate, and DOW CORNING® 4-6085, which showed clear solutions.
  • Nacure XP-297 - 0.1 % Increase cloudy, no residue.
  • Nacure XP-297 - 1 % Increase cloudy, no residue.
  • Phospholan PE65 - 0.1 % Increase cloudy, no residue.
  • Phospholan PE 169 - 1 % Increase very cloudy, no residue.
  • Tris(trimethylsilyl)phosphate - 1 % Increase hazy, no residue.
  • Tributylmethylammonium dibutyl very cloudy, clear oily droplets at phosphate - 5 % Increase surface
  • Samples were prepared according to the method of Reference Example 3 using ingredient (B l) a silanol terminated polydimethylsiloxane having a viscosity of 4000 cSt as the base polymer and 1.8 g of ingredient (C2) methyltriacetoxysilane as the crosslinker.
  • ingredient (B l) a silanol terminated polydimethylsiloxane having a viscosity of 4000 cSt as the base polymer and 1.8 g of ingredient (C2) methyltriacetoxysilane as the crosslinker.
  • the negative control which contained only ingredients (B l) and (C2)
  • each composition tested contained 1 % of the catalyst shown in the table below.
  • Phosphonitrile chloride INSTANTLY forms a glossy, rippled surface -dark brown staining.
  • Nacure 4054 1 hour smooth, clear, glossy.
  • Tributylammonium dibutyl >24 hours smooth, clear, glossy.
  • composition containing MTA The appearances of the composition containing MTA after 2 days are shown below in the table. Most of compositions increased in viscosity; only XP-297 gelled completely due to the catalyst being in water/IPA. The composition containing Phosphonitrile chloride had decreased in viscosity. All the samples appeared to be hazy, which may have been due to the solid MTA not being completely miscible in the compositions. Without wishing to be bound by theory, it is thought that this could be greatly reduced by using a mixture of
  • K-Cure 1040 1 hour smooth, slight haze, glossy.
  • DOW CORNING® 4-6085 45 min smooth, streaky, clear, and very glossy.
  • Nacure 1059 Slight Increase in Very cloudy, yellowy white, no viscosity residue.
  • Nacure XC 206 Increase in viscosity Clear with slight taint, no residue.
  • Phospholan PE65 Increase in viscosity Cloudy milky white, no residue.
  • Phospholan PE169 Increase in viscosity Cloudy milky white, no residue.
  • Nacure XC-9207 Increase in viscosity. Very slight haze, no residue.
  • Tributyl phosphate No change in viscosity. Slight haze, no residue.
  • Tris(trimethylsilyl) Increase in viscosity Cloudy white, with cloudy swirly phosphate streaks and blobs.
  • Nacure XP-333 Increase in viscosity. Cloudy white with some cloudy streaks
  • Nacure XC-C207 Increase in viscosity. Cloudy milky, no residue Catalyst Change in Viscosity Appearance of the uncured sample after 2 days
  • Mono-n-dodecyl Increase in viscosity. very hazy and milky, oily bloblets at phosphate bottom.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Silicon Polymers (AREA)
  • Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une composition qui est apte à durcir par une réaction de condensation. La composition utilise un catalyseur de réaction de condensation phosphonate. Le phosphonate est utilisé pour remplacer des catalyseurs classiques à l'étain. La composition peut réagir pour former une gomme, un gel ou un caoutchouc.
EP12710618.5A 2011-03-31 2012-03-12 Compositions contenant des catalyseurs phosphonates et procédés pour la préparation et l'utilisation des compositions Withdrawn EP2691175A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161469839P 2011-03-31 2011-03-31
PCT/US2012/028689 WO2012134784A1 (fr) 2011-03-31 2012-03-12 Compositions contenant des catalyseurs phosphonates et procédés pour la préparation et l'utilisation des compositions

Publications (1)

Publication Number Publication Date
EP2691175A1 true EP2691175A1 (fr) 2014-02-05

Family

ID=45879045

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12710618.5A Withdrawn EP2691175A1 (fr) 2011-03-31 2012-03-12 Compositions contenant des catalyseurs phosphonates et procédés pour la préparation et l'utilisation des compositions

Country Status (5)

Country Link
US (1) US20140039089A1 (fr)
EP (1) EP2691175A1 (fr)
JP (1) JP2014512948A (fr)
CN (1) CN103459027A (fr)
WO (1) WO2012134784A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140024774A1 (en) * 2011-03-31 2014-01-23 Simon Cook Condensation reaction curable silicone organic block copolymer composition containing a phosphonate catalyst and methods for the preparation and use of the composition
JP5852239B2 (ja) 2011-07-20 2016-02-03 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ 亜鉛含有錯体及び縮合反応触媒、この触媒を調製する方法、及びこの触媒を含有する組成物
CN103781850B (zh) 2011-09-07 2016-10-26 道康宁公司 含锆络合物和缩合反应催化剂、制备该催化剂的方法以及包含该催化剂的组合物
CN103781823B (zh) 2011-09-07 2016-08-17 道康宁公司 含钛络合物和缩合反应催化剂、制备该催化剂的方法以及包含该催化剂的组合物
US9328205B2 (en) 2011-10-04 2016-05-03 Dow Corning Corporation Iron(III) containing complex and condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
CN109679574B (zh) * 2019-01-16 2021-06-04 江西奋发科技有限公司 一种酸性有机硅涂覆胶及其制备方法
KR20230154957A (ko) * 2021-03-25 2023-11-09 가부시키가이샤 닛폰 쇼쿠바이 폴리실세스퀴옥산 조성물, 및, 경화물
US20230183426A1 (en) * 2021-12-13 2023-06-15 Novinium, Llc Aprotic catalysts for the hydrolysis / condensation of organoalkoxysilanes

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3654058A (en) * 1970-08-20 1972-04-04 Owens Illinois Inc Methods of curing organopolysiloxanes and laminates formed thereby
DE2653499C3 (de) * 1976-11-25 1980-05-08 Wacker-Chemie Gmbh, 8000 Muenchen Unter Ausschluß von Wasser lagerfähige bei Zutritt desselben bei Raumtemperatur zu Elastomeren vernetzende Organopolysiloxanformmassen
AU542909B2 (en) * 1980-02-25 1985-03-21 Minnesota Mining And Manufacturing Company Epoxypolysiloxane release coatings for adhesive materials
US4313988A (en) * 1980-02-25 1982-02-02 Minnesota Mining And Manufacturing Company Epoxypolysiloxane release coatings for adhesive materials
US4551515A (en) * 1984-02-27 1985-11-05 General Electric Company Process for the continuous manufacture of silicone gums
US5082706A (en) 1988-11-23 1992-01-21 Dow Corning Corporation Pressure sensitive adhesive/release liner laminate
DE4030727A1 (de) * 1990-09-28 1992-04-02 Eckart Standard Bronzepulver Kunstharzbeschichtete metallpigmente, verfahren zu ihrer herstellung und ihre verwendung
DE4302393A1 (de) * 1993-01-28 1994-08-04 Wacker Chemie Gmbh Zu Elastomeren vernetzende Organopolysiloxanmassen
DE19533915A1 (de) * 1995-09-13 1997-03-20 Bayer Ag Verfahren zur Herstellung von Poly(diorganosiloxanen) mit Diorganyloxyorganylsilyl- oder Triorganylsilyl-Endgruppen, vernetzbare Mischungen, enthaltend Poly(diorganosiloxane) mit Diorganyloxyorganylsilyl- oder Triorganyloxysilyl-Endgruppen und deren Verwendung
US5710300A (en) * 1997-04-11 1998-01-20 Dow Corning Corporation Siloxy phosphonate as stabilizing agent for polydiorganosiloxanes
US5962067A (en) * 1997-09-09 1999-10-05 Lucent Technologies Inc. Method for coating an article with a ladder siloxane polymer and coated article
DE19855619A1 (de) * 1998-12-02 2000-06-08 Wacker Chemie Gmbh Unter Abspaltung von Alkoholen zu Elastomeren vernetzbare Organopolysiloxanmassen
US6166170A (en) * 1999-12-02 2000-12-26 E. I. Du Pont De Nemours And Company Esterification catalysts and processes therefor and therewith
WO2007067332A2 (fr) 2005-12-08 2007-06-14 Dow Corning Corporation Procede continu pour la production d’adhesifs au silicone sensibles a la pression
US8071693B2 (en) * 2006-06-22 2011-12-06 Sabic Innovative Plastics Ip B.V. Polysiloxane/polyimide copolymers and blends thereof
WO2008005214A2 (fr) 2006-07-03 2008-01-10 Dow Corning Corporation Intercalaire à effet de bord et joint tout-en-un durcissant chimiquement
EP2065900A1 (fr) * 2007-10-23 2009-06-03 Borealis Technology Oy Composition polymère semi-conductrice
US9828404B2 (en) * 2008-05-05 2017-11-28 Douglas H. Adamson Crosslinked polymeric substrates methods of preparation and end use applications of the substrates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012134784A1 *

Also Published As

Publication number Publication date
CN103459027A (zh) 2013-12-18
WO2012134784A1 (fr) 2012-10-04
US20140039089A1 (en) 2014-02-06
JP2014512948A (ja) 2014-05-29

Similar Documents

Publication Publication Date Title
WO2012134788A1 (fr) Compositions contenant des catalyseurs phosphates et procédés pour la préparation et l'utilisation des compositions
EP2753655B1 (fr) Complexe contenant du titane et catalyseurs de réaction de condensation, procédés pour préparer ces catalyseurs et compositions contenant ces catalyseurs
US9469799B2 (en) Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts
EP2753663B1 (fr) Complexe contenant du zirconium et catalyseurs de réaction de condensation, procédés pour préparer ces catalyseurs et compositions contenant ces catalyseurs
EP2764053A1 (fr) Complexe contenant du fer(ii)et catalyseurs de réaction de condensation, procédés pour préparer ces catalyseurs et compositions contenant ces catalyseurs
EP2734298B1 (fr) Complexe contenant du zinc et catalyseurs de réaction de condensation, procédés pour préparer les catalyseurs, et compositions contenant les catalyseurs
WO2013013111A1 (fr) Complexe contenant de l'yttrium et catalyseurs de réaction de condensation, procédés pour préparer ces catalyseurs et compositions contenant ces catalyseurs
WO2012134784A1 (fr) Compositions contenant des catalyseurs phosphonates et procédés pour la préparation et l'utilisation des compositions
EP2691468A1 (fr) Compositions contenant des catalyseurs acides sulfoniques et procédés pour la préparation et l'utilisation des compositions
US20150210809A1 (en) Samarium Containing Complex and Condensation Reaction Catalysts, Methods for Preparing the Catalysts, and Compositions Containing the Catalysts
WO2013036550A1 (fr) Complexe contenant du hafnium et catalyseurs de réaction de condensation, procédés pour préparer ces catalyseurs et compositions contenant ces catalyseurs
EP2734588A1 (fr) Complexe contenant du cuivre, compositions pour réaction de condensation contenant ledit complexe et procédés de préparation et d'utilisation desdites compositions
WO2013009840A1 (fr) Complexes de lanthanides à ligands d'imidazole pour réactions de condensation
WO2013025887A2 (fr) Complexe contenant du bismuth et catalyseurs de réaction de condensation, procédés de préparation des catalyseurs et compositions contenant les catalyseurs
WO2013013109A1 (fr) Complexe contenant du germanium et compositions durcissables par réaction de condensation et procédés de préparation et d'utilisation de ces compositions
WO2013016508A1 (fr) Complexe contenant du nickel et catalyseurs de réaction de condensation, procédés de préparation des catalyseurs et compositions les contenant

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130904

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20161001